Use of Hydrogen and an Organozinc Compound for Polymerization and Polymer Property Control

ABSTRACT

Methods of controlling polymerization reactions using a synergistic amount of hydrogen and an organozinc compound are disclosed. The resulting polymers have lower molecular weights and higher melt flow indices.

BACKGROUND OF THE INVENTION

There are various methods and materials that can be employed to reducethe molecular weight and/or increase the melt flow index of anolefin-based polymer. For example, hydrogen can be used to producepolymers having lower molecular weights or higher melt indices. However,the use of excessive amounts of hydrogen may adversely affect thepolymerization process and other polymer properties.

It would be beneficial to develop new methods that can effectivelyreduce the molecular weight and/or increase the melt index of anolefin-based polymer without the use of excessive amounts of hydrogen,resulting in improved polymerization and polymer property control.Accordingly, it is to these ends that the present disclosure isdirected.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

Methods of controlling a polymerization reaction and for polymerizingolefins are disclosed herein. Generally, such methods employ the use ofboth hydrogen and an organozinc compound.

Consistent with aspects of the invention disclosed herein, a method ofcontrolling a polymerization reaction in a polymerization reactor systemcan comprise introducing a synergistic amount of hydrogen and anorganozinc compound into the polymerization reactor system to reduce aweight-average molecular weight (Mw) and/or to increase a melt index(MI) of an olefin polymer produced by the polymerization reaction. Thehydrogen and/or the organozinc compound can be introduced into apolymerization reactor within the polymerization reactor system, and/orthe hydrogen and/or the organozinc compound can be introduced into thepolymerization reaction system at a feed or inlet location other thandirectly into a polymerization reactor.

Another method of controlling a polymerization reaction in apolymerization reactor system is described herein, and in this aspect,the method can comprise:

-   -   (i) introducing a transition metal-based catalyst composition,        an olefin monomer, and optionally an olefin comonomer into a        polymerization reactor within the polymerization reactor system;    -   (ii) contacting the transition metal-based catalyst composition        with the olefin monomer and the optional olefin comonomer under        polymerization conditions to produce an olefin polymer; and    -   (iii) introducing a synergistic amount of hydrogen and an        organozinc compound into the polymerization reactor system to        reduce a Mw and/or to increase a MI of the olefin polymer.

In yet another aspect, an olefin polymerization process is disclosed.This process can comprise contacting a transition metal-based catalystcomposition with an olefin monomer and optionally an olefin comonomerunder polymerization conditions, and in the presence of a synergisticamount of hydrogen and an organozinc compound, to produce an olefinpolymer. In this process, a Mw of the olefin polymer can be less thanabout 200,000 g/mol and/or a MI of the olefin polymer can be greaterthan about 1 g/10 min.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects may bedirected to various feature combinations and sub-combinations describedin the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 presents a plot of the molecular weight distributions of thepolymers of Examples 1-2.

FIG. 2 presents a plot of the molecular weight distributions of thepolymers of Examples 3-5.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Regarding claim transitional terms or phrases, the transitional term“comprising,” which is synonymous with “including,” “containing,”“having,” or “characterized by,” is inclusive or open-ended and does notexclude additional, unrecited elements or method steps. The transitionalphrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The transitional phrase “consisting essentiallyof” limits the scope of a claim to the specified materials or steps andthose that do not materially affect the basic and novelcharacteristic(s) of the claim. A “consisting essentially of” claimoccupies a middle ground between closed claims that are written in a“consisting of” format and fully open claims that are drafted in a“comprising” format. Absent an indication to the contrary, describing acompound or composition as “consisting essentially of” is not to beconstrued as “comprising,” but is intended to describe the recitedcomponent that includes materials which do not significantly alter thecomposition or method to which the term is applied. For example, afeedstock consisting essentially of a material A can include impuritiestypically present in a commercially produced or commercially availablesample of the recited compound or composition. When a claim includesdifferent features and/or feature classes (for example, a method step,feedstock features, and/or product features, among other possibilities),the transitional terms comprising, consisting essentially of, andconsisting of apply only to the feature class to which it is utilized,and it is possible to have different transitional terms or phrasesutilized with different features within a claim. For example, a methodcan comprise several recited steps (and other non-recited steps), bututilize a system preparation consisting of specific components;alternatively, consisting essentially of specific components; oralternatively, comprising the specific components and other non-recitedcomponents. While compositions and methods are often described in termsof “comprising” various components or steps, the compositions andmethods can also “consist essentially of” or “consist of” the variouscomponents or steps, unless stated otherwise. For example, a catalystcomposition consistent with aspects of the present invention cancomprise; alternatively, can consist essentially of or alternatively,can consist of; (i) a transition metal compound, (ii) an activator, and(iii) optionally, a co-catalyst.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one. For instance, the disclosure of “anorganozinc compound,” “an olefin comonomer,” etc., is meant to encompassone, or mixtures or combinations of more than one, organozinc compound,olefin comonomer, etc., unless otherwise specified.

Groups of elements of the table are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements may be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any particular compound or group disclosed herein, any name orstructure (general or specific) presented is intended to encompass allconformational isomers, regioisomers, stereoisomers, and mixturesthereof that can arise from a particular set of substituents, unlessotherwise specified. The name or structure (general or specific) alsoencompasses all enantiomers, diastereomers, and other optical isomers(if there are any) whether in enantiomeric or racemic forms, as well asmixtures of stereoisomers, as would be recognized by a skilled artisan,unless otherwise specified. A general reference to pentane, for example,includes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane; and ageneral reference to a butyl group includes a n-butyl group, a sec-butylgroup, an iso-butyl group, and a t-butyl group.

Within this disclosure, the normal rules of organic nomenclature willprevail. For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is(are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4 position and hydrogens located at the 2, 3,5, and 6 positions. By way of another example, reference to a3-substituted naphth-2-yl indicates that there is a non-hydrogensubstituent located at the 3 position and hydrogens located at the 1, 4,5, 6, 7, and 8 positions. References to compounds or groups havingsubstitutions at positions in addition to the indicated position will bereferenced using comprising or some other alternative language. Forexample, a reference to a phenyl group comprising a substituent at the 4position refers to a phenyl group having a substituent at the 4 positionand hydrogen or any non-hydrogen substituent at the 2, 3, 5, and 6positions.

In an aspect, a chemical “group” is described according to how thatgroup is formally derived from a reference or “parent” compound, forexample, by the number of hydrogen atoms formally removed from theparent compound to generate the group, even if that group is notliterally synthesized in this manner. These groups can be utilized assubstituents or coordinated or bonded to metal atoms. By way of example,an “alkyl group” formally can be derived by removing one hydrogen atomfrom an alkane, while an “alkylene group” formally can be derived byremoving two hydrogen atoms from an alkane. Moreover, a more generalterm can be used to encompass a variety of groups that formally arederived by removing any number (“one or more”) hydrogen atoms from aparent compound, which in this example can be described as an “alkanegroup,” and which encompasses an “alkyl group,” an “alkylene group,” andmaterials have three or more hydrogen atoms, as necessary for thesituation, removed from the alkane. The disclosure that a substituent,ligand, or other chemical moiety may constitute a particular “group”implies that the well-known rules of chemical structure and bonding arefollowed when that group is employed as described. When describing agroup as being “derived by,” “derived from,” “formed by,” or “formedfrom,” such terms are used in a formal sense and are not intended toreflect any specific synthetic methods or procedure, unless specifiedotherwise or the context requires otherwise.

The term “substituted” when used to describe a group or a chain ofcarbon atoms, for example, when referring to a substituted analog of aparticular group or chain, is intended to describe or group or chainwherein any non-hydrogen moiety formally replaces a hydrogen in thatgroup or chain, and is intended to be non-limiting, unless statedotherwise. A group or chain also can be referred to herein as“unsubstituted” or by equivalent terms such as “non-substituted,” whichrefers to the original group or chain. “Substituted” is intended to benon-limiting and can include hydrocarbon substituents as specified andas understood by one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g., halogenated hydrocarbon indicates thepresence of one or more halogen atoms replacing an equivalent number ofhydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” is usedherein in accordance with the definition specified by IUPAC: a univalentgroup formed by removing a hydrogen atom from a hydrocarbon (that is, agroup containing only carbon and hydrogen). Similarly, a “hydrocarbylenegroup” refers to a group formed by removing two hydrogen atoms from ahydrocarbon, either two hydrogen atoms from one carbon atom or onehydrogen atom from each of two different carbon atoms. Therefore, inaccordance with the terminology used herein, a “hydrocarbon group”refers to a generalized group formed by removing one or more hydrogenatoms (as needed for the particular group) from a hydrocarbon. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” canbe acyclic or cyclic groups, and/or can be linear or branched. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” caninclude rings, ring systems, aromatic rings, and aromatic ring systems,which contain only carbon and hydrogen. “Hydrocarbyl groups,”“hydrocarbylene groups,” and “hydrocarbon groups” include, by way ofexample, aryl, arylene, arene groups, alkyl, alkylene, alkane groups,cycloalkyl, cycloalkylene, cycloalkane groups, aralkyl, aralkylene, andaralkane groups, respectively, among other groups as members.

An aliphatic compound is a non-aromatic organic compound. An “aliphaticgroup” is a generalized group formed by removing one or more hydrogenatoms (as needed for the particular group) from the carbon atoms of analiphatic compound. An aliphatic compound can be acyclic or cyclic,saturated or unsaturated, and/or linear or branched organic compound.Aliphatic compounds and aliphatic groups can contain organic functionalgroup(s) and/or atom(s) other than carbon and hydrogen unless otherwisespecified (e.g., an aliphatic hydrocarbon).

An “aromatic group” refers to a generalized group formed by removing oneor more hydrogen atoms (as needed for the particular group and at leastone of which is an aromatic ring carbon atom) from an aromatic compound.Thus, an “aromatic group” as used herein refers to a group derived byremoving one or more hydrogen atoms from an aromatic compound, that is,a compound containing a cyclically conjugated hydrocarbon that followsthe Hückel (4n+2) rule and containing (4n+2) pi-electrons, where n is aninteger from 1 to about 5. Aromatic compounds and hence “aromaticgroups” can be monocyclic or polycyclic unless otherwise specified.Aromatic compounds include “arenes” (hydrocarbon aromatic compounds),examples of which can include, but are not limited to, benzene,naphthalene, and toluene, among others. As disclosed herein, the term“substituted” can be used to describe an aromatic group wherein anynon-hydrogen moiety formally replaces a hydrogen in that group, and isintended to be non-limiting, unless stated otherwise.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).The term “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or may be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl group are derived by removal of a hydrogen atom from a primary,secondary, tertiary carbon atom, respectively, of an alkane. The n-alkylgroup may be derived by removal of a hydrogen atom from a terminalcarbon atom of a linear alkane. The groups RCH₂ (R≠H), R₂CH(R≠H), andR₃C(R≠H) are primary, secondary, and tertiary alkyl groups,respectively.

A cycloalkane is a saturated cyclic hydrocarbon, with or without sidechains (e.g., cyclobutane or methylcyclobutane). Unsaturated cyclichydrocarbons having at least one non-aromatic endocyclic carbon-carbondouble or one triple bond are cycloalkenes and cycloalkynes,respectively. Unsaturated cyclic hydrocarbons having more than one suchmultiple bond can further specify the number and/or position(s) of suchmultiple bonds (e.g., cycloalkadienes, cycloalkatrienes, and so forth).The unsaturated cyclic hydrocarbons can be further identified by theposition of the carbon-carbon multiple bond(s).

A “cycloalkyl group” is a univalent group derived by removing a hydrogenatom from a ring carbon atom from a cycloalkane. For example, a1-methylcyclopropyl group and a 2-methylcyclopropyl group areillustrated as follows:

A “cycloalkylene group” refers to a group derived by removing twohydrogen atoms from a cycloalkane, at least one of which is a ringcarbon. Thus, a “cycloalkylene group” includes a group derived from acycloalkane in which two hydrogen atoms are formally removed from thesame ring carbon, a group derived from a cycloalkane in which twohydrogen atoms are formally removed from two different ring carbons, anda group derived from a cycloalkane in which a first hydrogen atom isformally removed from a ring carbon and a second hydrogen atom isformally removed from a carbon atom that is not a ring carbon. A“cycloalkane group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is a ring carbon) from a cycloalkane.

The term “alkene” whenever used in this specification and claims refersto a compound that has at least one non-aromatic carbon-carbon doublebond. The term “alkene” includes aliphatic or aromatic, cyclic oracyclic, and/or linear and branched alkenes unless expressly statedotherwise. Alkenes can also be further identified by the position of thecarbon-carbon double bond. Alkenes having more than one such multiplebond are alkadienes, alkatrienes, and so forth. The alkene can befurther identified by the position(s) of the carbon-carbon doublebond(s).

An “alkenyl group” is a univalent group derived from an alkene byremoval of a hydrogen atom from any carbon atom of the alkene. Thus,“alkenyl group” includes groups in which the hydrogen atom is formallyremoved from an sp² hybridized (olefinic) carbon atom and groups inwhich the hydrogen atom is formally removed from any other carbon atom.For example and unless otherwise specified, propen-1-yl (—CH═CHCH₃),propen-2-yl [(CH₃)C═CH₂], and propen-3-yl (—CH₂CH═CH₂) groups are allencompassed with the term “alkenyl group.” Similarly, an “alkenylenegroup” refers to a group formed by formally removing two hydrogen atomsfrom an alkene, either two hydrogen atoms from one carbon atom or onehydrogen atom from two different carbon atoms. An “alkene group” refersto a generalized group formed by removing one or more hydrogen atoms (asneeded for the particular group) from an alkene. When the hydrogen atomis removed from a carbon atom participating in a carbon-carbon doublebond, the regiochemistry of the carbon from which the hydrogen atom isremoved, and regiochemistry of the carbon-carbon double bond can both bespecified. Alkenyl groups can also have more than one such multiplebond. The alkene group can also be further identified by the position(s)of the carbon-carbon double bond(s).

The term “alkyne” is used in this specification and claims to refer to acompound that has at least one carbon-carbon triple bond. The term“alkyne” includes aliphatic or aromatic, cyclic or acyclic, and/orlinear and branched alkynes unless expressly stated otherwise. Alkyneshaving more than one such multiple bond are alkadiynes, alkatriynes, andso forth. The alkyne group can also be further identified by theposition(s) of the carbon-carbon triple bond(s).

An “alkynyl group” is a univalent group derived from an alkyne byremoval of a hydrogen atom from any carbon atom of the alkyne. Thus,“alkynyl group” includes groups in which the hydrogen atom is formallyremoved from an sp hybridized (acetylenic) carbon atom and groups inwhich the hydrogen atom is formally removed from any other carbon atom.For example and unless otherwise specified, 1-propyn-1-yl (—C≡CCH₃) andpropyn-3-yl (HC≡CCH₂—) groups are encompassed with the term “alkynylgroup.” Similarly, an “alkynylene group” refers to a group formed byformally removing two hydrogen atoms from an alkyne, either two hydrogenatoms from one carbon atom if possible or one hydrogen atom from twodifferent carbon atoms. An “alkyne group” refers to a generalized groupformed by removing one or more hydrogen atoms (as needed for theparticular group) from an alkyne. Alkyne groups can have more than onesuch multiple bond. Alkyne groups can also be further identified by theposition(s) of the carbon-carbon triple bond(s).

An “aryl group” refers to a generalized group formed by removing ahydrogen atom from an aromatic hydrocarbon ring carbon atom from anarene. One example of an “aryl group” is ortho-tolyl (o-tolyl), thestructure of which is shown here.

Similarly, an “arylene group” refers to a group formed by removing twohydrogen atoms (at least one of which is from an aromatic hydrocarbonring carbon) from an arene. An “arene group” refers to a generalizedgroup formed by removing one or more hydrogen atoms (as needed for theparticular group and at least one of which is an aromatic hydrocarbonring carbon) from an arene.

An “aralkyl group” is an aryl-substituted alkyl group having a freevalance at a non-aromatic carbon atom, for example, a benzyl group is an“aralkyl” group. Similarly, an “aralkylene group” is an aryl-substitutedalkylene group having two free valances at a single non-aromatic carbonatom or a free valence at two non-aromatic carbon atoms while an“aralkane group” is a generalized is an aryl-substituted alkane grouphaving one or more free valances at a non-aromatic carbon atom(s).

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth. A copolymer can bederived from an olefin monomer and one olefin comonomer, while aterpolymer can be derived from an olefin monomer and two olefincomonomers. Accordingly, “polymer” encompasses copolymers, terpolymers,etc., derived from any olefin monomer and comonomer(s) disclosed herein.Similarly, an ethylene polymer would include ethylene homopolymers,ethylene copolymers, ethylene terpolymers, and the like. As an example,an olefin copolymer, such as an ethylene copolymer, can be derived fromethylene and a comonomer, such as 1-butene, 1-hexene, or 1-octene. Ifthe monomer and comonomer were ethylene and 1-hexene, respectively, theresulting polymer could be categorized an as ethylene/1-hexenecopolymer. The term “polymer” also is meant to include all molecularweight polymers, and is inclusive of lower molecular weight polymers oroligomers. Applicants intend for the term “polymer” to encompassoligomers derived from any olefin monomer disclosed herein (as well froman olefin monomer and one olefin comonomer, an olefin monomer and twoolefin comonomers, and so forth).

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc., as wellas processes that might also be referred to as oligomerizationprocesses. Therefore, a copolymerization process would involvecontacting an olefin monomer (e.g., ethylene) and an olefin comonomer(e.g., 1-hexene) to produce an olefin copolymer.

The term “synergistic amount” of hydrogen and an organozinc compound isused herein to indicate that the combined addition (whether fedseparately or in combination) of hydrogen and an organozinc compound hasa “synergistic effect” on certain properties of the polymer, i.e., theeffect of the addition of the synergistic amount of the two differentcomponents is greater than the effect of each component individually,and moreover, is greater than the sum of the individual componenteffects.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organomagnesiumcompounds, organolithium compounds, and the like, that can constituteone component of a catalyst composition, when used in addition to anactivator-support. The term “co-catalyst” is used regardless of theactual function of the compound or any chemical mechanism by which thecompound may operate.

The terms “chemically-treated solid oxide,” “treated solid oxidecompound,” and the like, are used herein to indicate a solid, inorganicoxide of relatively high porosity, which can exhibit Lewis acidic orBrønsted acidic behavior, and which has been treated with anelectron-withdrawing component, typically an anion, and which iscalcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the chemically-treatedsolid oxide can comprise a calcined contact product of at least onesolid oxide with at least one electron-withdrawing anion sourcecompound. Typically, the chemically-treated solid oxide comprises atleast one acidic solid oxide compound. The “activator-support” of thepresent invention can be a chemically-treated solid oxide. The terms“support” and “activator-support” are not used to imply these componentsare inert, and such components should not be construed as an inertcomponent of the catalyst composition. The term “activator,” as usedherein, refers generally to a substance that is capable of converting atransition metal component into a catalyst that can polymerize olefins,or converting a contact product of a transition metal compound and acomponent that provides an activatable ligand (e.g., an alkyl, ahydride) to the transition metal compound, when the transition metalcompound does not already comprise such a ligand, into a catalyst thatcan polymerize olefins. This term is used regardless of the actualactivating mechanism. Illustrative activators includeactivator-supports, aluminoxanes, organoboron or organoborate compounds,ionizing ionic compounds, and the like. Aluminoxanes, organoboron ororganoborate compounds, and ionizing ionic compounds generally arereferred to as activators if used in a catalyst composition in which anactivator-support is not present. If the catalyst composition containsan activator-support, then the aluminoxane, organoboron or organoborate,and ionizing ionic materials are typically referred to as co-catalysts.

The term “fluoroorgano boron compound” is used herein with its ordinarymeaning to refer to neutral compounds of the form BY₃. The term“fluoroorgano borate compound” also has its usual meaning to refer tothe monoanionic salts of a fluoroorgano boron compound of the form[cation]⁺[BY₄]⁻, where Y represents a fluorinated organic group.Materials of these types are generally and collectively referred to as“organoboron or organoborate compounds.”

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of theclaimed catalyst composition/mixture/system, the nature of the activecatalytic site, or the fate of the co-catalyst, the transition metalcompound(s), any olefin monomer used to prepare a precontacted mixture,or the activator (e.g., activator-support), after combining thesecomponents. Therefore, the terms “catalyst composition,” “catalystmixture,” “catalyst system,” and the like, encompass the initialstarting components of the composition, as well as whatever product(s)may result from contacting these initial starting components, and thisis inclusive of both heterogeneous and homogenous catalyst systems orcompositions.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions described herein. Combining additional materials orcomponents can be done by any suitable method. Further, the term“contact product” includes mixtures, blends, solutions, slurries,reaction products, and the like, or combinations thereof. Although“contact product” can include reaction products, it is not required forthe respective components to react with one another. Similarly, the term“contacting” is used herein to refer to materials which may be blended,mixed, slurried, dissolved, reacted, treated, or otherwise contacted insome other manner.

The term “precontacted” mixture is used herein to describe a firstmixture of catalyst components that are contacted for a first period oftime prior to the first mixture being used to form a “postcontacted” orsecond mixture of catalyst components that are contacted for a secondperiod of time. Typically, the precontacted mixture can describe amixture of transition metal compound (one or more than one), olefinmonomer (or monomers), and organoaluminum compound (or compounds),before this mixture is contacted with an activator-support(s) andoptional additional organoaluminum compound. Thus, precontacteddescribes components that are used to contact each other, but prior tocontacting the components in the second, postcontacted mixture.Accordingly, this invention may occasionally distinguish between acomponent used to prepare the precontacted mixture and that componentafter the mixture has been prepared. For example, according to thisdescription, it is possible for the precontacted organoaluminumcompound, once it is contacted with the transition metal compound andthe olefin monomer, to have reacted to form at least one differentchemical compound, formulation, or structure from the distinctorganoaluminum compound used to prepare the precontacted mixture. Inthis case, the precontacted organoaluminum compound or component isdescribed as comprising an organoaluminum compound that was used toprepare the precontacted mixture.

Additionally, the precontacted mixture can describe a mixture oftransition metal compound(s) and organoaluminum compound(s), prior tocontacting this mixture with an activator-support(s). This precontactedmixture also can describe a mixture of transition metal compound(s),olefin monomer(s), and activator-support(s), before this mixture iscontacted with an organoaluminum co-catalyst compound or compounds.

Similarly, the term “postcontacted” mixture is used herein to describe asecond mixture of catalyst components that are contacted for a secondperiod of time, and one constituent of which is the “precontacted” orfirst mixture of catalyst components that were contacted for a firstperiod of time. Typically, the term “postcontacted” mixture is usedherein to describe the mixture of transition metal compound(s), olefinmonomer(s), organoaluminum compound(s), and activator-support(s) formedfrom contacting the precontacted mixture of a portion of thesecomponents with any additional components added to make up thepostcontacted mixture. Often, the activator-support can comprise achemically-treated solid oxide. For instance, the additional componentadded to make up the postcontacted mixture can be a chemically-treatedsolid oxide (one or more than one), and optionally, can include anorganoaluminum compound which is the same as or different from theorganoaluminum compound used to prepare the precontacted mixture, asdescribed herein. Accordingly, this invention may also occasionallydistinguish between a component used to prepare the postcontactedmixture and that component after the mixture has been prepared.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention. The publications discussed throughout the text are providedsolely for their disclosure prior to the filing date of the presentapplication. Nothing herein is to be construed as an admission that theinventors are not entitled to antedate such disclosure by virtue ofprior invention.

Applicants disclose several types of ranges in the present invention.When Applicants disclose or claim a range of any type, Applicants'intent is to disclose or claim individually each possible number thatsuch a range could reasonably encompass, including end points of therange as well as any sub-ranges and combinations of sub-rangesencompassed therein. For example, when the Applicants disclose or claima chemical moiety having a certain number of carbon atoms, Applicants'intent is to disclose or claim individually every possible number thatsuch a range could encompass, consistent with the disclosure herein. Forexample, the disclosure that a moiety is a C₁ to C₁₈ hydrocarbyl group,or in alternative language a hydrocarbyl group having from 1 to 18carbon atoms, as used herein, refers to a moiety that can be selectedindependently from a hydrocarbyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as any rangebetween these two numbers (for example, a C₁ to C₈ hydrocarbyl group),and also including any combination of ranges between these two numbers(for example, a C₂ to C₄ and a C₆ to C₁₂ hydrocarbyl group).

Similarly, another representative example follows for the molar ratio ofhydrogen to olefin monomer provided in aspects of this invention. By adisclosure that the molar ratio of the hydrogen to olefin monomer can bein a range from about 0.01:1 to 0.2:1, Applicants intend to recite thatthe molar ratio can be 0.01:1, about 0.02:1, about 0.03:1, about 0.04:1,about 0.05:1, about 0.06:1, about 0.07:1, about 0.08:1, about 0.09:1,about 0.1:1, about 0.11:1, about 0.12:1, about 0.13:1, about 0.14:1,about 0.15:1, about 0.16:1, about 0.17:1, about 0.18:1, about 0.19:1, orabout 0.2:1. Additionally, the molar ratio can be within any range fromabout 0.01:1 to about 0.2:1 (for example, the molar ratio can be in arange from about 0.02:1 to about 0.1:1), and this also includes anycombination of ranges between about 0.01:1 and about 0.2:1. Likewise,all other ranges disclosed herein should be interpreted in a mannersimilar to these examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants can be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants canbe unaware of at the time of the filing of the application.

The following abbreviations, among others, are used in this disclosure:

-   -   DEZ—diethylzinc    -   Et—ethyl    -   HLMI—high load melt index    -   Me—methyl    -   MI—melt index    -   Mw—weight-average molecular weight    -   Ph—phenyl    -   TIBA—triisobutylaluminum

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein are methods for controlling a polymerization reactionin a polymerization reactor system. Processes for the polymerization ofolefins also are described.

Methods Utilizing Hydrogen and an Organozinc Compound

Various aspects of the present invention are directed to methods ofcontrolling a polymerization reaction in a polymerization reactorsystem. For instance, a method of controlling a polymerization reactionin a polymerization reactor system can comprise a step of introducing asynergistic amount of hydrogen and an organozinc compound into thepolymerization reactor system to reduce a weight-average molecularweight (Mw) and/or to increase a melt index (MI) of an olefin polymerproduced by the polymerization reaction. Another method disclosed hereinfor controlling a polymerization reaction in a polymerization reactorsystem can comprise:

-   -   (i) introducing a transition metal-based catalyst composition,        an olefin monomer, and optionally an olefin comonomer into a        polymerization reactor within the polymerization reactor system;    -   (ii) contacting the transition metal-based catalyst composition        with the olefin monomer and the optional olefin comonomer under        polymerization conditions to produce an olefin polymer; and    -   (iii) introducing a synergistic amount of hydrogen and an        organozinc compound into the polymerization reactor system to        reduce a Mw and/or to increase a MI of the olefin polymer.

In these methods, the hydrogen and the organozinc compound can beintroduced (e.g., added, injected, etc.) into the polymerization reactorsystem by any suitable means, either alone, with a carrier (e.g., acarrier gas, a carrier liquid, etc.), in combination, etc. In someaspects, the hydrogen and the organozinc compound can be introduced intothe polymerization reactor system at different locations within thesystem, although this is not a requirement. Additionally, the hydrogenand the organozinc compound often can be added directly into apolymerization reactor within the polymerization reactor system.However, in some aspects, one or more of the hydrogen and the organozinccompound can be introduced into the polymerization reaction system at afeed or inlet location other than directly into a polymerizationreactor, for example, in a recycle stream. In one aspect, hydrogen canbe added to the polymerization reactor along with the olefin monomerfeed, while in another aspect, hydrogen can be added to thepolymerization reactor separate from the olefin monomer feed. In anotheraspect, the organozinc compound can be added to the reactor by itself,while in yet another aspect, the organozinc compound can be added to thereactor with a carrier or solvent, non-limiting examples of which caninclude, but are not limited to isobutane, n-butane, n-pentane,isopentane, neopentane, n-hexane, heptane, octane, cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, benzene, toluene,xylene, ethylbenzene, and the like, or combinations thereof.

Generally, the features of the methods disclosed herein (e.g., thetransition metal-based catalyst composition, the olefin monomer, theolefin polymer, the organozinc compound, the synergistic amount ofhydrogen and the organozinc compound, the polymerization reactor, theMw, the MI, among others) are independently described herein, and thesefeatures may be combined in any combination to further describe thedisclosed methods.

In certain methods disclosed herein, a step can comprise introducing atransition metal-based catalyst composition, an olefin monomer, andoptionally an olefin comonomer into the polymerization reactor. As wouldbe recognized by one of skill in the art, additional components can beintroduced into the polymerization reactor in addition to the transitionmetal-based catalyst composition and the olefin monomer (and, olefincomonomer(s), if desired), and such unrecited components are encompassedherein. For instance, in the operation of a polymerization reactorsystem—depending, of course, on the polymerization reactor type, thedesired olefin polymer, etc., among other factors—solvents and/ordiluents and/or fluidizing gases, recycle streams, etc., also can beadded or introduced into the polymerization reactor and polymerizationreactor system.

As one of ordinary skill in the art would recognize, hydrogen can begenerated in-situ by transition metal catalyst compositions in variousolefin polymerization processes, and the amount generated may varydepending upon the specific catalyst composition and transition metalcompound(s) employed, the type of polymerization process used, thepolymerization reaction conditions utilized, and so forth. In accordancewith the present invention, hydrogen is added to the polymerizationreactor system (e.g., into a polymerization reactor). For example,hydrogen can be added as a set mole or weight percentage of the olefinmonomer, and fed continuously to the reactor system along with themonomer. In one aspect, hydrogen can be added to the reactor system at ahydrogen:olefin monomer molar ratio in a range from about 0.005:1 toabout 0.3:1, or from about 0.007:1 to about 0.25:1. In another aspect,hydrogen can be added to the reactor system at a hydrogen:olefin monomermolar ratio in a range from about 0.01:1 to about 0.2:1. Yet, in anotheraspect, hydrogen can be added to the reactor system at a hydrogen:olefinmonomer molar ratio in a range from about 0.02:1 to about 0.2:1;alternatively, from about 0.01:1 to about 0.19:1; alternatively, fromabout 0.02:1 to about 0.18:1; alternatively, from about 0.03:1 to about0.17:1; alternatively, from about 0.04:1 to about 0.16:1; oralternatively, from about 0.05:1 to about 0.15:1.

In some aspects of this invention, the feed ratio of hydrogen to olefinmonomer can be maintained substantially constant during thepolymerization run for a particular polymer grade. That is, thehydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from, for example, about 0.01:1 to about 0.2:1, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 0.1:1, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the molar ratio between about 0.075:1 and about 0.125:1.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

In accordance with the present invention, an organozinc compound can beadded to the polymerization reactor system (e.g., into a polymerizationreactor), either alone or with a carrier. In one aspect, the addition ofthe organozinc compound can result in a concentration of the organozinccompound in a range from about 0.02 mmol/L to about 2.5 mmol/L, based onthe total volume of liquid in the reactor (e.g., slurry reactor,solution reactor). In another aspect, the organozinc addition can resultin a concentration in a range from about 0.02 to about 2.2 mmol/L, fromabout 0.02 mmol/L to about 2 mmol/L, from about 0.03 mmol/L to about 2mmol/L, or from about 0.03 to about 1.8 mmol/L. In yet another aspect,the resulting organozinc concentration can be in a range from about 0.03to about 1.7 mmol/L; alternatively, from about 0.04 to about 2 mmol/L;alternatively, from about 0.05 to about 2 mmol/L; alternatively, fromabout 0.03 to about 1.5 mmol/L; alternatively, from about 0.03 to about1.2 mmol/L; alternatively, from about 0.02 to about 1 mmol/L;alternatively, from about 0.05 to about 2 mmol/L; or from about 0.05 toabout 1.5 mmol/L.

In an aspect, hydrogen and/or the organozinc compound can be introducedin the polymerization reactor system continuously. Alternatively,hydrogen and/or the organozinc compound (and/or monomer and/or optionalcomonomer) can be periodically pulsed to the reactor, for instance, in amanner similar to that employed in U.S. Pat. No. 5,739,220 and U.S.Patent Publication No. 2004/0059070, the disclosures of which areincorporated herein by reference in their entirety.

Hydrogen can be introduced into the polymerization reactor systembefore, during, and/or after the addition of the organozinc compound.For instance, hydrogen and the organozinc compound can be introducedinto the reactor system substantially simultaneously. Such can beaccomplished by the continuous addition of both components, or pulsedaddition of both components at substantially the same time.Alternatively, hydrogen can be introduced into the reactor system beforeand/or after the addition of the organozinc compound, but not atsubstantially the same time.

Regardless of the manner in which hydrogen and the organozinc compoundare added to the polymerization reactor system (i.e., relative timing,order of addition, location within the system, periodic or continuousaddition, with or without a carrier, etc.), a synergistic amount ofhydrogen and the organozinc compound can be added to the polymerizationreactor system. The synergistic combination of these materials canresult in a reduction in Mw and/or an increase in MI of an olefinpolymer produced in the polymerization reactor system. While not beinglimited thereto, Applicants nevertheless contemplate various synergisticamounts or combinations of hydrogen and the organozinc compound. In someaspects, the synergistic amount of hydrogen and the organozinc compoundcan comprise a hydrogen:organozinc compound molar ratio in a range fromabout 100:1 to about 25,000:1. Accordingly, contemplatedhydrogen:organozinc compound molar ratios can include, but are notlimited to, the following ranges: from about 100:1 to about 20,000:1,from about 100:1 to about 10,000:1, from about 100:1 to about 7, 500:1,from about 100:1 to about 5,000:1, from about 200:1 to about 20,000:1,from about 250:1 to about 20,000:1, from about 250:1 to about 15,000:1,from about 300:1 to about 20,000:1, from about 300:1 to about 10,000:1,from about 300:1 to about 5,000:1, from about 1,000:1 to about 7, 500:1,from about 500:1 to about 7, 500:1, from about 500:1 to about 5,000:1,and so forth.

The addition of a synergistic amount of hydrogen and an organozinccompound can reduce a Mw and/or increase a MI of an olefin polymer. Forexample, the Mw of the olefin polymer produced can be reduced to lessthan about 250,000, less than about 225,000, or less than about 200,000g/mol. In some aspects, the Mw of the olefin polymer can be reduced toless than about 190,000, less than about 180,000, less than about170,000, less than about 160,000, or less than about 150,000 g/mol.Contemplated Mw ranges encompassed by the present invention can include,but are not limited to, from about 40,000 to about 250,000 g/mol, fromabout 50,000 to about 250,000 g/mol, from about 40,000 to about 200,000g/mol, from about 50,000 to about 200,000 g/mol, from about 70,000 toabout 225,000 g/mol, from about 70,000 to about 170,000 g/mol, fromabout 60,000 to about 210,000 g/mol, from about 60,000 to about 180,000g/mol, or from about 80,000 to about 160,000 g/mol.

The addition of a synergistic amount of hydrogen and an organozinccompound can result in a significant reduction in the Mw (or Mz, or Mv,or Mp) of an olefin polymer, as compared to the Mw (or Mz, or Mv, or Mp)of an olefin polymer produced in the absence of hydrogen and theorganozinc compound. In one aspect, the Mw (or Mz, or Mv, or Mp) of theolefin polymer can be reduced by at least about 50%, at least about 60%,at least about 70%, or at least about 75%. In further aspects, the Mw(or Mz, or Mv, or Mp) of an olefin polymer can be reduced by at leastabout 80%; alternatively, at least about 85%; or alternatively, at leastabout 90%. Additionally, the ratio of Mw/Mn of the olefin polymer alsocan be reduced by at least about 50%, at least about 70%, at least about75%, at least about 80%, at least about 85%, or at least about 90%, viathe addition of the synergistic amount of hydrogen and the organozinccompound.

Interestingly, while the Mw (or Mz, or Mv, or Mp) can be reducedsignificantly by the introduction of the synergistic amount of hydrogenand the organozinc compound, the Mn of the olefin polymer can besubstantially unchanged. That is, the Mn of an olefin polymer producedusing a synergistic amount of hydrogen and the organozinc compound canbe within +/−25% (and in some aspects, +/−20%, or +/−15%) of the Mn ofan olefin polymer produced in the absence of hydrogen and the organozinccompound.

The addition of a synergistic amount of hydrogen and an organozinccompound can result in a significant increase in the MI (or HLMI) of anolefin polymer, as compared to the MI (or HLMI) of an olefin polymerproduced in the absence of hydrogen and the organozinc compound. In oneaspect, the MI can be increased to at least about 0.75 g/10 min, whilein another aspect, the MI can be increased to at least about 1 g/10 min.Contemplated MI ranges encompassed by the present invention can include,but are not limited to, from about 1 to about 50 g/10 min, from about 1to about 25 g/10 min, from about 1 to about 20 g/10 min, from about 1.5to about 20 g/10 min, from about 2 to about 15 g/10 min, from about 2.5to about 25 g/10 min, from about 3 to about 10 g/10 min, from about 1 toabout 10 g/10 min, or from about 1.5 to about 8 g/10 min.

In another aspect of this invention, olefin polymerization processes aredisclosed. One such process can comprise contacting a transitionmetal-based catalyst composition with an olefin monomer and optionallyan olefin comonomer under polymerization conditions (e.g., in apolymerization reactor system), and in the presence of a synergisticamount of hydrogen and an organozinc compound (or introducing asynergistic amount of hydrogen and the organozinc compound into apolymerization reactor system), to produce an olefin polymer. In thisprocess, a Mw of the olefin polymer can be less than about 200,000 g/moland/or a MI of the olefin polymer can be greater than about 1 g/10 min.

Generally, the features of these olefin polymerization processes (e.g.,the transition metal-based catalyst composition, the olefin monomer, theolefin polymer, the organozinc compound, the synergistic amount ofhydrogen and the organozinc compound, the Mw, the MI, etc.) areindependently described herein, and these features may be combined inany combination to further describe the disclosed processes. Forexample, the transition metal-based catalyst composition can be achromium-based catalyst composition, a Ziegler-Natta based catalystcomposition, a metallocene-based catalyst composition, or a combinationthereof; or alternatively, the transition metal-based catalystcomposition can comprise any transition metal compound disclosed herein,e.g., comprising at least one of chromium, vanadium, titanium,zirconium, and hafnium; any activator disclosed herein, e.g., anactivator-support, an aluminoxane, etc; and optionally, any co-catalystdisclosed herein, e.g., an organoaluminum compound. Likewise, the olefinmonomer can be any olefin monomer disclosed herein, such as a C₂-C₂₀olefin, or ethylene; and the olefin comonomer can be any comonomerdisclosed herein, such as propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-decene, styrene, and the like, or mixturesthereof. The presence of a synergistic amount of hydrogen and theorganozinc compound (or the introduction of a synergistic amount ofhydrogen and the organozinc compound) can encompass any molar amount ofhydrogen:organozinc compound disclosed herein, such as within a range offrom about 100:1 to about 25,000:1, from about 200:1 to about 20,000:1,or from about 500:1 to about 7, 500:1.

In such olefin polymerization processes, the Mw of the olefin polymergenerally can be less than about 200,000 g/mol, such as within a rangefrom about 50,000 to about 200,000 g/mol. Additionally or alternatively,the MI of the olefin polymer generally can be greater than about 1 g/10min, such as within a range from about 1 to about 20 g/10 min.

For ethylene-based polymers produced herein, the density typically canfall within the range from about 0.88 to about 0.97 g/cc. In one aspectof this invention, the ethylene polymer density can be in a range fromabout 0.90 to about 0.97 g/cc. Yet, in another aspect, the densitygenerally can be in a range from about 0.91 to about 0.96 g/cc.

Polymers of ethylene, whether homopolymers, copolymers, terpolymers, andso forth, can be formed into various articles of manufacture. Articleswhich can comprise polymers of this invention include, but are notlimited to, an agricultural film, an automobile part, a bottle, a drum,a fiber or fabric, a food packaging film or container, a food servicearticle, a fuel tank, a geomembrane, a household container, a liner, amolded product, a medical device or material, a pipe, a sheet or tape, atoy, and the like. Various processes can be employed to form thesearticles. Non-limiting examples of these processes can include injectionmolding, blow molding, rotational molding, film extrusion, sheetextrusion, profile extrusion, thermoforming, and the like. Additionally,additives and modifiers are often added to these polymers in order toprovide beneficial polymer processing or end-use product attributes.Such processes and materials are described in Modern PlasticsEncyclopedia, Mid-November 1995 Issue, Vol. 72, No. 12; and FilmExtrusion Manual—Process, Materials, Properties, TAPPI Press, 1992; thedisclosures of which are incorporated herein by reference in theirentirety.

Applicants also contemplate a method for forming or preparing an articleof manufacture comprising a polymer produced by any of thepolymerization processes disclosed herein. For instance, a method cancomprise (i) contacting a transition metal-based catalyst compositionwith an olefin monomer and optionally an olefin comonomer (one or more)under polymerization conditions, and in the presence of a synergisticamount of hydrogen and an organozinc compound (or introducing asynergistic amount of hydrogen and the organozinc compound into apolymerization reactor system), to produce an olefin polymer, wherein aMw of the olefin polymer can be less than about 200,000 g/mol and/or aMI of the olefin polymer can be greater than about 1 g/10 min; and (ii)forming an article of manufacture comprising the olefin polymer. Theforming step can comprise blending, melt processing, extruding, molding,or thermoforming, and the like, including combinations thereof.

Organozinc Compounds

Organozinc compounds suitable for use in the present invention caninclude, but are not limited to, compounds having the formula:

Zn(X¹⁰)(X¹¹)  (I).

Generally, the selections of X¹⁰ and X¹¹ in formula (I) areindependently described herein, and these selections can be combined inany combination to further describe the organozinc compound havingformula (I). In some aspects, X¹⁰ can be a C₁ to C₁₈ hydrocarbyl group,and X¹¹ can be H, a halide, or a C₁ to C₁₈ hydrocarbyl or C₁ to C₁₈hydrocarboxy group. It is contemplated in these and other aspects thatX¹⁰ and X¹¹ can be the same, or that X¹⁰ and X¹¹ can be different.

In one aspect, X¹⁰ and X¹¹ independently can be a C₁ to C₁₈ hydrocarbylgroup, while in another aspect, X¹⁰ and X¹¹ independently can be a C₁ toC₁₂ hydrocarbyl group. In yet another aspect, X¹⁰ and X¹¹ independentlycan be a C₁ to C₈ hydrocarbyl group or a C₁ to C₅ hydrocarbyl group. Instill another aspect, X¹⁰ and X¹¹ independently can be a C₁ to C₁₈ alkylgroup, a C₂ to C₁₈ alkenyl group, a C₆ to C₁₈ aryl group, or a C₇ to C₁₈aralkyl group. In these and other aspects, X¹⁰ and X¹¹ independently canbe a C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenyl group, a C₆ to C₁₅ arylgroup, or a C₇ to C₁₅ aralkyl group; alternatively, X¹⁰ and X¹¹independently can be a C₁ to C₁₀ alkyl group, a C₂ to C₁₀ alkenyl group,a C₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group; alternatively, X¹⁰and X¹¹ independently can be a C₁ to C₈ alkyl group, a C₂ to C₈ alkenylgroup, a C₆ to C₁₀ aryl group, or a C₇ to C₁₀ aralkyl group; oralternatively, X¹⁰ and X¹¹ independently can be a C₁ to C₅ alkyl group,a C₂ to C₅ alkenyl group, a C₆ to C₈ aryl group, or a C₇ to C₈ aralkylgroup.

Accordingly, in some aspects, the alkyl group which can be X¹⁰ and/orX¹¹ in formula (I) can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, a undecyl group, a dodecylgroup, a tridecyl group, a tetradecyl group, a pentadecyl group, ahexadecyl group, a heptadecyl group, or an octadecyl group; oralternatively, a methyl group, an ethyl group, a propyl group, a butylgroup, a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, or a decyl group. In other aspects, the alkyl group whichcan be X¹⁰ and/or X¹¹ in formula (I) can be a methyl group, an ethylgroup, a n-propyl group, an iso-propyl group, a n-butyl group, aniso-butyl group, a sec-butyl group, a tert-butyl group, a n-pentylgroup, an iso-pentyl group, a sec-pentyl group, or a neopentyl group;alternatively, a methyl group, an ethyl group, an iso-propyl group, an-butyl group, a tert-butyl group, or a neopentyl group; alternatively,a methyl group; alternatively, an ethyl group; alternatively, a n-propylgroup; alternatively, an iso-propyl group; alternatively, a n-butylgroup; alternatively, a tert-butyl group; or alternatively, a neopentylgroup.

Illustrative alkenyl groups which can be X¹⁰ and/or X¹¹ in formula (I)can include, but are not limited to, an ethenyl group, a propenyl group,a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a undecenyl group, adodecenyl group, a tridecenyl group, a tetradecenyl group, apentadecenyl group, a hexadecenyl group, a heptadecenyl group, or anoctadecenyl group. In one aspect, X¹⁰ and/or X¹¹ in formula (I) can bean ethenyl group, a propenyl group, a butenyl group, a pentenyl group, ahexenyl group, a heptenyl group, an octenyl group, a nonenyl group, or adecenyl group, while in another aspect, X¹⁰ and/or X¹¹ can be an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, or a hexenylgroup. For example, X¹⁰ and/or X¹¹ can be an ethenyl group;alternatively, a propenyl group; alternatively, a butenyl group;alternatively, a pentenyl group; or alternatively, a hexenyl group. Inyet another aspect, X¹⁰ and/or X¹¹ can be an acyclic terminal alkenylgroup, such as a C₃ to C₁₀, or a C₃ to C₈, terminal alkenyl group.

In some aspects, the aryl group which can be X¹⁰ and/or X¹¹ in formula(I) can be a phenyl group, a substituted phenyl group, a naphthyl group,or a substituted naphthyl group. In an aspect, the aryl group can be aphenyl group or a substituted phenyl group; alternatively, a naphthylgroup or a substituted naphthyl group; alternatively, a phenyl group ora naphthyl group; or alternatively, a substituted phenyl group or asubstituted naphthyl group. Substituents which can be utilized for thesubstituted phenyl group or substituted naphthyl group are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the substituted phenyl group or substituted naphthyl groupwhich can be utilized as X¹⁰ and/or X¹¹ in formula (I).

In an aspect, the substituted phenyl group which can be utilized as X¹⁰and/or X¹¹ can be a 2-substituted phenyl group, a 3-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other aspects, the substitutedphenyl group can be a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, 3,5-disubstituted phenylgroup; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents which can be utilized for these specific substituted phenylgroups are independently disclosed herein and can be utilized withoutlimitation to further describe these substituted phenyl groups which canbe utilized as the X¹⁰ and/or X¹¹ group of formula (I).

In some aspects, the aralkyl group which can be utilized as X¹⁰ and/orX¹¹ of formula (I) can be a benzyl group or a substituted benzyl group.Substituents which can be utilized for the substituted aralkyl group areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted aralkyl group which can be utilized asX¹⁰ and/or X¹¹ of formula (I).

In an aspect, each non-hydrogen substituent for the substituted arylgroup or substituted aralkyl group which can be X¹⁰ and/or X¹¹ informula (I) independently can be a C₁ to C₁₀ hydrocarbyl group;alternatively, a C₁ to C₈ hydrocarbyl group; or alternatively, a C₁ toC₅ hydrocarbyl group. Specific substituent hydrocarbyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituents of the substituted aryl group orsubstituted aralkyl group which can be X¹⁰ and/or X¹¹ of formula (I).The number of substituents and their respective number of carbon atomsin any substituted aryl group or substituted aralkyl group is limitedsuch that X¹⁰ and X¹¹ of formula (I) have at most 18 carbon atoms.Exemplary hydrocarbyl substituents can include, but are not limited to,an alkyl group, such as a methyl group, an ethyl group, a n-propylgroup, an isopropyl group, a n-butyl group, a sec-butyl group, anisobutyl group, a tert-butyl group, a n-pentyl group, a 2-pentyl group,a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group,and the like, including combinations thereof.

In one aspect, X¹⁰ and X¹¹ independently can be a C₁ to C₁₂ alkyl group,a C₂ to C₁₂ alkenyl group, a C₆ to C₁₅ aryl group, or a C₇ to C₁₅aralkyl group; or alternatively, a C₁ to C₈ alkyl group, a C₂ to C₈alkenyl group, a C₆ to C₁₀ aryl group, or a C₇ to C₁₀ aralkyl group. Inanother aspect, X¹⁰ and X¹¹ in independently can be a C₁ to C₁₂ alkylgroup or a C₂ to C₁₂ alkenyl group. In yet another aspect, X¹⁰ and X¹¹independently can be methyl, ethyl, propyl, butyl, pentyl (e.g.,neopentyl), hexyl, heptyl, octyl, nonyl, decyl, ethenyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl,benzyl, or tolyl; alternatively, methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl,heptenyl, octenyl, phenyl, benzyl, or tolyl; alternatively, methyl,ethyl, propyl, butyl, pentyl, hexyl, ethenyl, propenyl, butenyl,pentenyl, hexenyl, phenyl, benzyl, or tolyl; or alternatively, methyl,ethyl, propyl, butyl, pentyl, ethenyl, propenyl, butenyl, or pentenyl.In still another aspect, X¹⁰ and X¹¹ independently can be methyl, ethyl,propyl, butyl, or pentyl (e.g., neopentyl), or both X¹⁰ and X¹¹ can bemethyl, or ethyl, or propyl, or butyl, or pentyl (e.g., neopentyl).

In some aspects, X¹¹ can be a C₁ to C₁₈ hydrocarboxy group. Ahydrocarboxy group is used generically herein to include, for instance,alkoxy, aryloxy, aralkoxy, and -(alkyl, aryl, or aralyl)-O-(alkyl, aryl,or aralkyl) groups, and such groups which are suitable for X¹¹ cancomprise up to about 18 carbon atoms (e.g., C₁ to C₁₈, C₁ to C₁₂, C₁ toC₁₀, or C₁ to C₈ hydrocarboxy groups). Illustrative and non-limitingexamples of hydrocarboxy groups which can be X¹¹ in formula (I) caninclude, but are not limited to, a methoxy group, an ethoxy group, an-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxygroup, an isobutoxy group, a tert-butoxy group, a n-pentoxy group, a2-pentoxy group, a 3-pentoxy group, a 2-methyl-1-butoxy group, atert-pentoxy group, a 3-methyl-1-butoxy group, a 3-methyl-2-butoxygroup, a neo-pentoxy group, a phenoxy group, a toloxy group, a xyloxygroup, a 2,4,6-trimethylphenoxy group, a benzoxy group, anacetylacetonate group (acac), and the like. In an aspect, thehydrocarboxy group which can be X¹¹ in formula (I) can be a methoxygroup; alternatively, an ethoxy group; alternatively, a n-propoxy group;alternatively, an isopropoxy group; alternatively, a n-butoxy group;alternatively, a sec-butoxy group; alternatively, an isobutoxy group;alternatively, a tert-butoxy group; alternatively, a n-pentoxy group;alternatively, a 2-pentoxy group; alternatively, a 3-pentoxy group;alternatively, a 2-methyl-1-butoxy group; alternatively, a tert-pentoxygroup; alternatively, a 3-methyl-1-butoxy group, alternatively, a3-methyl-2-butoxy group; alternatively, a neo-pentoxy group;alternatively, a phenoxy group; alternatively, a toloxy group;alternatively, a xyloxy group; alternatively, a 2,4,6-trimethylphenoxygroup; alternatively, a benzoxy group; or alternatively, anacetylacetonate group.

X¹¹ can be H, a halide, or a C₁ to C₁₈ hydrocarbyl or C₁ to C₁₈hydrocarboxy group. In some aspects, X¹¹ can be H, a halide (e.g., Cl),or a C₁ to C₁₂ hydrocarbyl or C₁ to C₁₂ hydrocarboxy group;alternatively, H, a halide, or a C₁ to C₈ hydrocarbyl or C₁ to C₈hydrocarboxy group; or alternatively, H, Br, Cl, F, I, methyl, ethyl,propyl, butyl, pentyl (e.g., neopentyl), hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, benzyl, tolyl, methoxy, ethoxy, propoxy,butoxy pentoxy, phenoxy, toloxy, xyloxy, or benzoxy.

In certain aspects, the organozinc compound can be adi(hydrocarbylsilyl)zinc compound. Each hydrocarbyl (one or more) of thehydrocarbylsilyl group can be any hydrocarbyl group disclosed herein(e.g., a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenyl group, a C₆ to C₁₈aryl group, a C₇ to C₁₈ aralkyl group, etc.). Illustrative andnon-limiting examples of hydrocarbylsilyl groups can include, but arenot limited to, trimethylsilyl, triethylsilyl, tripropylsilyl (e.g.,triisopropylsilyl), tributylsilyl, tripentylsilyl, triphenylsilyl,allyldimethylsilyl, trimethylsilylmethyl, and the like.

In other aspects, the organozinc compound can be dimethylzinc,diethylzinc, dipropylzinc, dibutylzinc, dineopentylzinc,di(trimethylsilyl)zinc, di(triethylsilyl)zinc,di(triisoproplysilyl)zinc, di(triphenylsilyl)zinc,di(allyldimethylsilyl)zinc, di(trimethylsilylmethyl)zinc, and the like,or combinations thereof; alternatively, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc,di(trimethylsilylmethyl)zinc, or combinations thereof; alternatively,dimethylzinc; alternatively, diethylzinc; alternatively, dipropylzinc;alternatively, dibutylzinc; alternatively, dineopentylzinc; oralternatively, di(trimethylsilylmethyl)zinc.

Activator-Supports

The present invention encompasses various catalyst compositionscontaining an activator-support. In one aspect, the activator-supportcan comprise a chemically-treated solid oxide. Alternatively, in anotheraspect, the activator-support can comprise a clay mineral, a pillaredclay, an exfoliated clay, an exfoliated clay gelled into another oxidematrix, a layered silicate mineral, a non-layered silicate mineral, alayered aluminosilicate mineral, a non-layered aluminosilicate mineral,or combinations thereof.

Generally, chemically-treated solid oxides exhibit enhanced acidity ascompared to the corresponding untreated solid oxide compound. Thechemically-treated solid oxide also can function as a catalyst activatoras compared to the corresponding untreated solid oxide. While thechemically-treated solid oxide can activate a transition metal complexin the absence of co-catalysts, it is not necessary to eliminateco-catalysts from the catalyst composition. The activation function ofthe activator-support may be evident in the enhanced activity ofcatalyst composition as a whole, as compared to a catalyst compositioncontaining the corresponding untreated solid oxide. However, it isbelieved that the chemically-treated solid oxide can function as anactivator, even in the absence of organoaluminum compounds,aluminoxanes, organoboron or organoborate compounds, ionizing ioniccompounds, and the like.

The chemically-treated solid oxide can comprise a solid oxide treatedwith an electron-withdrawing anion. While not intending to be bound bythe following statement, it is believed that treatment of the solidoxide with an electron-withdrawing component augments or enhances theacidity of the oxide. Thus, either the activator-support exhibits Lewisor Brønsted acidity that is typically greater than the Lewis or Brønstedacid strength of the untreated solid oxide, or the activator-support hasa greater number of acid sites than the untreated solid oxide, or both.One method to quantify the acidity of the chemically-treated anduntreated solid oxide materials can be by comparing the polymerizationactivities of the treated and untreated oxides under acid catalyzedreactions.

Chemically-treated solid oxides of this invention generally can beformed from an inorganic solid oxide that exhibits Lewis acidic orBrønsted acidic behavior and has a relatively high porosity. The solidoxide can be chemically-treated with an electron-withdrawing component,typically an electron-withdrawing anion, to form an activator-support.

According to one aspect of the present invention, the solid oxide usedto prepare the chemically-treated solid oxide can have a pore volumegreater than about 0.1 cc/g. According to another aspect of the presentinvention, the solid oxide can have a pore volume greater than about 0.5cc/g. According to yet another aspect of the present invention, thesolid oxide can have a pore volume greater than about 1.0 cc/g.

In another aspect, the solid oxide can have a surface area of from about100 to about 1000 m²/g. In yet another aspect, the solid oxide can havea surface area of from about 200 to about 800 m²/g. In still anotheraspect of the present invention, the solid oxide can have a surface areaof from about 250 to about 600 m²/g.

The chemically-treated solid oxide can comprise a solid inorganic oxidecomprising oxygen and one or more elements selected from Group 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, orcomprising oxygen and one or more elements selected from the lanthanideor actinide elements (See: Hawley's Condensed Chemical Dictionary,11^(th) Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G.,Murillo, C. A., and Bochmann, M., Advanced Inorganic Chemistry, 6^(th)Ed., Wiley-Interscience, 1999). For example, the inorganic oxide cancomprise oxygen and an element, or elements, selected from Al, B, Be,Bi, Cd, Co, Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V,W, P, Y, Zn, and Zr.

Suitable examples of solid oxide materials or compounds that can be usedto form the chemically-treated solid oxide can include, but are notlimited to, Al₂O₃, B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃,Ga₂O₃, La₂O₃, Mn₂O₃, MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂,TiO₂, V₂O₅, WO₃, Y₂O₃, ZnO, ZrO₂, and the like, including mixed oxidesthereof, and combinations thereof. For example, the solid oxide cancomprise silica, alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, titania,zirconia, magnesia, boria, zinc oxide, mixed oxides thereof, or anycombination thereof.

The solid oxide of this invention encompasses oxide materials such asalumina, “mixed oxide” compounds thereof such as silica-alumina, andcombinations and mixtures thereof. The mixed oxide compounds such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form a solid oxide compound. Examplesof mixed oxides that can be used in the activator-support of the presentinvention, either singly or in combination, can include, but are notlimited to, silica-alumina, silica-titania, silica-zirconia, zeolites,various clay minerals, alumina-titania, alumina-zirconia,zinc-aluminate, alumina-boria, silica-boria, aluminophosphate-silica,titania-zirconia, and the like. The solid oxide of this invention alsoencompasses oxide materials such as silica-coated alumina, as describedin U.S. Pat. No. 7,884,163, the disclosure of which is incorporatedherein by reference in its entirety.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspectof the present invention, the electron-withdrawing component can be anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anions caninclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, and the like, including mixtures andcombinations thereof. In addition, other ionic or non-ionic compoundsthat serve as sources for these electron-withdrawing anions also can beemployed in the present invention. It is contemplated that theelectron-withdrawing anion can be, or can comprise, fluoride, chloride,bromide, phosphate, triflate, bisulfate, or sulfate, and the like, orany combination thereof, in some aspects of this invention. In otheraspects, the electron-withdrawing anion can comprise sulfate, bisulfate,fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate,phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or combinations thereof.

Thus, for example, the activator-support (e.g., chemically-treated solidoxide) used in the catalyst compositions of the present invention canbe, or can comprise, fluorided alumina, chlorided alumina, bromidedalumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, or combinations thereof.In one aspect, the activator-support can be, or can comprise, fluoridedalumina, sulfated alumina, fluorided silica-alumina, sulfatedsilica-alumina, fluorided silica-coated alumina, sulfated silica-coatedalumina, phosphated silica-coated alumina, and the like, or anycombination thereof. In another aspect, the activator-support cancomprise fluorided alumina; alternatively, chlorided alumina;alternatively, sulfated alumina; alternatively, fluoridedsilica-alumina; alternatively, sulfated silica-alumina; alternatively,fluorided silica-zirconia; alternatively, chlorided silica-zirconia; oralternatively, fluorided silica-coated alumina.

When the electron-withdrawing component comprises a salt of anelectron-withdrawing anion, the counterion or cation of that salt can beselected from any cation that allows the salt to revert or decomposeback to the acid during calcining. Factors that dictate the suitabilityof the particular salt to serve as a source for the electron-withdrawinganion can include, but are not limited to, the solubility of the salt inthe desired solvent, the lack of adverse reactivity of the cation,ion-pairing effects between the cation and anion, hygroscopic propertiesimparted to the salt by the cation, and the like, and thermal stabilityof the anion. Examples of suitable cations in the salt of theelectron-withdrawing anion can include, but are not limited to,ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkylphosphonium, H⁺, [H(OEt₂)₂]⁺, and the like.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the activator-support to the desired level. Combinations ofelectron-withdrawing components can be contacted with the oxide materialsimultaneously or individually, and in any order that affords thedesired chemically-treated solid oxide acidity. For example, one aspectof this invention can employ two or more electron-withdrawing anionsource compounds in two or more separate contacting steps.

Thus, a process by which a chemically-treated solid oxide can beprepared is as follows: a selected solid oxide, or combination of solidoxides, can be contacted with a first electron-withdrawing anion sourcecompound to form a first mixture; this first mixture can be calcined andthen contacted with a second electron-withdrawing anion source compoundto form a second mixture; the second mixture then can be calcined toform a treated solid oxide. In such a process, the first and secondelectron-withdrawing anion source compounds can be either the same ordifferent compounds.

According to another aspect of the present invention, thechemically-treated solid oxide can comprise a solid inorganic oxidematerial, a mixed oxide material, or a combination of inorganic oxidematerials, that is chemically-treated with an electron-withdrawingcomponent, and optionally treated with a metal source, including metalsalts, metal ions, or other metal-containing compounds. Non-limitingexamples of the metal or metal ion can include zinc, nickel, vanadium,titanium, silver, copper, gallium, tin, tungsten, molybdenum, zirconium,and the like, or combinations thereof. Examples of chemically-treatedsolid oxides that contain a metal or metal ion can include, but are notlimited to, chlorided zinc-impregnated alumina, fluoridedtitanium-impregnated alumina, fluorided zinc-impregnated alumina,chlorided zinc-impregnated silica-alumina, fluorided zinc-impregnatedsilica-alumina, sulfated zinc-impregnated alumina, chlorided zincaluminate, fluorided zinc aluminate, sulfated zinc aluminate,silica-coated alumina treated with hexafluorotitanic acid, silica-coatedalumina treated with zinc and then fluorided, and the like, or anycombination thereof.

Any method of impregnating the solid oxide material with a metal can beused. The method by which the oxide is contacted with a metal source,typically a salt or metal-containing compound, can include, but is notlimited to, gelling, co-gelling, impregnation of one compound ontoanother, and the like. If desired, the metal-containing compound can beadded to or impregnated into the solid oxide in solution form, andsubsequently converted into the supported metal upon calcining.Accordingly, the solid inorganic oxide can further comprise a metalselected from zinc, titanium, nickel, vanadium, silver, copper, gallium,tin, tungsten, molybdenum, and the like, or combinations of thesemetals. For example, zinc often can be used to impregnate the solidoxide because it can provide improved catalyst activity at a low cost.

The solid oxide can be treated with metal salts or metal-containingcompounds before, after, or at the same time that the solid oxide istreated with the electron-withdrawing anion. Following any contactingmethod, the contacted mixture of solid compound, electron-withdrawinganion, and the metal ion can be calcined. Alternatively, a solid oxidematerial, an electron-withdrawing anion source, and the metal salt ormetal-containing compound can be contacted and calcined simultaneously.

Various processes can be used to form the chemically-treated solid oxideuseful in the present invention. The chemically-treated solid oxide cancomprise the contact product of one or more solid oxides with one ormore electron-withdrawing anion sources. It is not required that thesolid oxide be calcined prior to contacting the electron-withdrawinganion source. Typically, the contact product can be calcined eitherduring or after the solid oxide is contacted with theelectron-withdrawing anion source. The solid oxide can be calcined oruncalcined. Various processes to prepare solid oxide activator-supportsthat can be employed in this invention have been reported. For example,such methods are described in U.S. Pat. Nos. 6,107,230, 6,165,929,6,294,494, 6,300,271, 6,316,553, 6,355,594, 6,376,415, 6,388,017,6,391,816, 6,395,666, 6,524,987, 6,548,441, 6,548,442, 6,576,583,6,613,712, 6,632,894, 6,667,274, and 6,750,302, the disclosures of whichare incorporated herein by reference in their entirety.

According to one aspect of the present invention, the solid oxidematerial can be chemically-treated by contacting it with anelectron-withdrawing component, typically an electron-withdrawing anionsource. Further, the solid oxide material optionally can be chemicallytreated with a metal ion, and then calcined to form a metal-containingor metal-impregnated chemically-treated solid oxide. According toanother aspect of the present invention, the solid oxide material andelectron-withdrawing anion source can be contacted and calcinedsimultaneously.

The method by which the oxide is contacted with the electron-withdrawingcomponent, typically a salt or an acid of an electron-withdrawing anion,can include, but is not limited to, gelling, co-gelling, impregnation ofone compound onto another, and the like. Thus, following any contactingmethod, the contacted mixture of the solid oxide, electron-withdrawinganion, and optional metal ion, can be calcined.

The solid oxide activator-support (i.e., chemically-treated solid oxide)thus can be produced by a process comprising:

1) contacting a solid oxide (or solid oxides) with anelectron-withdrawing anion source compound (or compounds) to form afirst mixture; and

2) calcining the first mixture to form the solid oxideactivator-support.

According to another aspect of the present invention, the solid oxideactivator-support (chemically-treated solid oxide) can be produced by aprocess comprising:

1) contacting a solid oxide (or solid oxides) with a firstelectron-withdrawing anion source compound to form a first mixture;

2) calcining the first mixture to produce a calcined first mixture;

3) contacting the calcined first mixture with a secondelectron-withdrawing anion source compound to form a second mixture; and

4) calcining the second mixture to form the solid oxideactivator-support.

According to yet another aspect of the present invention, thechemically-treated solid oxide can be produced or formed by contactingthe solid oxide with the electron-withdrawing anion source compound,where the solid oxide compound is calcined before, during, or aftercontacting the electron-withdrawing anion source, and where there is asubstantial absence of aluminoxanes, organoboron or organoboratecompounds, and ionizing ionic compounds.

Calcining of the treated solid oxide generally can be conducted in anambient atmosphere, typically in a dry ambient atmosphere, at atemperature from about 200° C. to about 900° C., and for a time of about1 minute to about 100 hours. Calcining can be conducted at a temperatureof from about 300° C. to about 800° C., or alternatively, at atemperature of from about 400° C. to about 700° C. Calcining can beconducted for about 30 minutes to about 50 hours, or for about 1 hour toabout 15 hours. Thus, for example, calcining can be carried out forabout 1 to about 10 hours at a temperature of from about 350° C. toabout 550° C. Any suitable ambient atmosphere can be employed duringcalcining. Generally, calcining can be conducted in an oxidizingatmosphere, such as air. Alternatively, an inert atmosphere, such asnitrogen or argon, or a reducing atmosphere, such as hydrogen or carbonmonoxide, can be used.

According to one aspect of the present invention, the solid oxidematerial can be treated with a source of halide ion, sulfate ion, or acombination of anions, optionally treated with a metal ion, and thencalcined to provide the chemically-treated solid oxide in the form of aparticulate solid. For example, the solid oxide material can be treatedwith a source of sulfate (termed a “sulfating agent”), a source ofchloride ion (termed a “chloriding agent”), a source of fluoride ion(termed a “fluoriding agent”), or a combination thereof, and calcined toprovide the solid oxide activator. Useful acidic activator-supports caninclude, but are not limited to, bromided alumina, chlorided alumina,fluorided alumina, sulfated alumina, bromided silica-alumina, chloridedsilica-alumina, fluorided silica-alumina, sulfated silica-alumina,bromided silica-zirconia, chlorided silica-zirconia, fluoridedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,alumina treated with hexafluorotitanic acid, silica-coated aluminatreated with hexafluorotitanic acid, silica-alumina treated withhexafluorozirconic acid, silica-alumina treated with trifluoroaceticacid, fluorided boria-alumina, silica treated with tetrafluoroboricacid, alumina treated with tetrafluoroboric acid, alumina treated withhexafluorophosphoric acid, a pillared clay, such as a pillaredmontmorillonite, optionally treated with fluoride, chloride, or sulfate;phosphated alumina or other aluminophosphates optionally treated withsulfate, fluoride, or chloride; or any combination of the above.Further, any of these activator-supports optionally can be treated orimpregnated with a metal ion.

The chemically-treated solid oxide can comprise a fluorided solid oxidein the form of a particulate solid. The fluorided solid oxide can beformed by contacting a solid oxide with a fluoriding agent. The fluorideion can be added to the oxide by forming a slurry of the oxide in asuitable solvent such as alcohol or water including, but not limited to,the one to three carbon alcohols because of their volatility and lowsurface tension. Examples of suitable fluoriding agents can include, butare not limited to, hydrofluoric acid (HF), ammonium fluoride (NH₄F),ammonium bifluoride (NH₄HF₂), ammonium tetrafluoroborate (NH₄BF₄),ammonium silicofluoride (hexafluorosilicate) ((NH₄)₂SiF₆), ammoniumhexafluorophosphate (NH₄PF₆), hexafluorotitanic acid (H₂TiF₆), ammoniumhexafluorotitanic acid ((NH₄)₂TiF₆), hexafluorozirconic acid (H₂ZrF₆),AlF₃, NH₄AlF₄, analogs thereof, and combinations thereof. Triflic acidand ammonium triflate also can be employed. For example, ammoniumbifluoride (NH₄HF₂) can be used as the fluoriding agent, due to its easeof use and availability.

If desired, the solid oxide can be treated with a fluoriding agentduring the calcining step. Any fluoriding agent capable of thoroughlycontacting the solid oxide during the calcining step can be used. Forexample, in addition to those fluoriding agents described previously,volatile organic fluoriding agents can be used. Examples of volatileorganic fluoriding agents useful in this aspect of the invention caninclude, but are not limited to, freons, perfluorohexane,perfluorobenzene, fluoromethane, trifluoroethanol, and the like, andcombinations thereof. Calcining temperatures generally must be highenough to decompose the compound and release fluoride. Gaseous hydrogenfluoride (HF) or fluorine (F₂) itself also can be used with the solidoxide if fluorided while calcining. Silicon tetrafluoride (SiF₄) andcompounds containing tetrafluoroborate (BF₄ ⁻) also can be employed. Oneconvenient method of contacting the solid oxide with the fluoridingagent can be to vaporize a fluoriding agent into a gas stream used tofluidize the solid oxide during calcination.

Similarly, in another aspect of this invention, the chemically-treatedsolid oxide can comprise a chlorided solid oxide in the form of aparticulate solid. The chlorided solid oxide can be formed by contactinga solid oxide with a chloriding agent. The chloride ion can be added tothe oxide by forming a slurry of the oxide in a suitable solvent. Thesolid oxide can be treated with a chloriding agent during the calciningstep. Any chloriding agent capable of serving as a source of chlorideand thoroughly contacting the oxide during the calcining step can beused, such as SiCl₄, SiMe₂Cl₂, TiCl₄, BCl₃, and the like, includingmixtures thereof. Volatile organic chloriding agents can be used.Examples of suitable volatile organic chloriding agents can include, butare not limited to, certain freons, perchlorobenzene, chloromethane,dichloromethane, chloroform, carbon tetrachloride, trichloroethanol, andthe like, or any combination thereof. Gaseous hydrogen chloride orchlorine itself also can be used with the solid oxide during calcining.One convenient method of contacting the oxide with the chloriding agentcan be to vaporize a chloriding agent into a gas stream used to fluidizethe solid oxide during calcination.

The amount of fluoride or chloride ion present before calcining thesolid oxide generally can be from about 1 to about 50% by weight, wherethe weight percent is based on the weight of the solid oxide, forexample, silica-alumina, before calcining. According to another aspectof this invention, the amount of fluoride or chloride ion present beforecalcining the solid oxide can be from about 1 to about 25% by weight,and according to another aspect of this invention, from about 2 to about20% by weight. According to yet another aspect of this invention, theamount of fluoride or chloride ion present before calcining the solidoxide can be from about 4 to about 10% by weight. Once impregnated withhalide, the halided oxide can be dried by any suitable method including,but not limited to, suction filtration followed by evaporation, dryingunder vacuum, spray drying, and the like, although it is also possibleto initiate the calcining step immediately without drying theimpregnated solid oxide.

The silica-alumina used to prepare the treated silica-alumina typicallycan have a pore volume greater than about 0.5 cc/g. According to oneaspect of the present invention, the pore volume can be greater thanabout 0.8 cc/g, and according to another aspect of the presentinvention, greater than about 1.0 cc/g. Further, the silica-aluminagenerally can have a surface area greater than about 100 m²/g. Accordingto another aspect of this invention, the surface area can be greaterthan about 250 m²/g. Yet, in another aspect, the surface area can begreater than about 350 m²/g.

The silica-alumina utilized in the present invention typically can havean alumina content from about 5 to about 95% by weight. According to oneaspect of this invention, the alumina content of the silica-alumina canbe from about 5 to about 50%, or from about 8% to about 30%, alumina byweight. In another aspect, high alumina content silica-alumina compoundscan be employed, in which the alumina content of these silica-aluminacompounds typically ranges from about 60% to about 90%, or from about65% to about 80%, alumina by weight. According to yet another aspect ofthis invention, the solid oxide component can comprise alumina withoutsilica, and according to another aspect of this invention, the solidoxide component can comprise silica without alumina.

The sulfated solid oxide can comprise sulfate and a solid oxidecomponent, such as alumina or silica-alumina, in the form of aparticulate solid. Optionally, the sulfated oxide can be treated furtherwith a metal ion such that the calcined sulfated oxide comprises ametal. According to one aspect of the present invention, the sulfatedsolid oxide can comprise sulfate and alumina. In some instances, thesulfated alumina can be formed by a process wherein the alumina istreated with a sulfate source, for example, sulfuric acid or a sulfatesalt such as ammonium sulfate. This process generally can be performedby forming a slurry of the alumina in a suitable solvent, such asalcohol or water, in which the desired concentration of the sulfatingagent has been added. Suitable organic solvents can include, but are notlimited to, the one to three carbon alcohols because of their volatilityand low surface tension.

According to one aspect of this invention, the amount of sulfate ionpresent before calcining can be from about 0.5 to about 100 parts byweight sulfate ion to about 100 parts by weight solid oxide. Accordingto another aspect of this invention, the amount of sulfate ion presentbefore calcining can be from about 1 to about 50 parts by weight sulfateion to about 100 parts by weight solid oxide, and according to stillanother aspect of this invention, from about 5 to about 30 parts byweight sulfate ion to about 100 parts by weight solid oxide. Theseweight ratios are based on the weight of the solid oxide beforecalcining Once impregnated with sulfate, the sulfated oxide can be driedby any suitable method including, but not limited to, suction filtrationfollowed by evaporation, drying under vacuum, spray drying, and thelike, although it is also possible to initiate the calcining stepimmediately.

According to another aspect of the present invention, theactivator-support used in preparing the catalyst compositions of thisinvention can comprise an ion-exchangeable activator-support including,but not limited to, silicate and aluminosilicate compounds or minerals,either with layered or non-layered structures, and combinations thereof.In another aspect of this invention, ion-exchangeable, layeredaluminosilicates such as pillared clays can be used asactivator-supports. When the acidic activator-support comprises anion-exchangeable activator-support, it can optionally be treated with atleast one electron-withdrawing anion such as those disclosed herein,though typically the ion-exchangeable activator-support is not treatedwith an electron-withdrawing anion.

According to another aspect of the present invention, theactivator-support of this invention can comprise clay minerals havingexchangeable cations and layers capable of expanding. Typical claymineral activator-supports can include, but are not limited to,ion-exchangeable, layered aluminosilicates such as pillared clays.Although the term “support” is used, it is not meant to be construed asan inert component of the catalyst composition, but rather can beconsidered an active part of the catalyst composition, because of itsintimate association with the transition metal complex component.

According to another aspect of the present invention, the clay materialsof this invention can encompass materials either in their natural stateor that have been treated with various ions by wetting, ion exchange, orpillaring. Typically, the clay material activator-support of thisinvention can comprise clays that have been ion exchanged with largecations, including polynuclear, highly charged metal complex cations.However, the clay material activator-supports of this invention also canencompass clays that have been ion exchanged with simple salts,including, but not limited to, salts of Al(III), Fe(II), Fe(III), andZn(II) with ligands such as halide, acetate, sulfate, nitrate, ornitrite.

According to another aspect of the present invention, theactivator-support can comprise a pillared clay. The term “pillared clay”is used to refer to clay materials that have been ion exchanged withlarge, typically polynuclear, highly charged metal complex cations.Examples of such ions can include, but are not limited to, Keggin ionswhich can have charges such as 7+, various polyoxometallates, and otherlarge ions. Thus, the term pillaring can refer to a simple exchangereaction in which the exchangeable cations of a clay material arereplaced with large, highly charged ions, such as Keggin ions. Thesepolymeric cations then can be immobilized within the interlayers of theclay and when calcined are converted to metal oxide “pillars,”effectively supporting the clay layers as column-like structures. Thus,once the clay is dried and calcined to produce the supporting pillarsbetween clay layers, the expanded lattice structure can be maintainedand the porosity can be enhanced. The resulting pores can vary in shapeand size as a function of the pillaring material and the parent claymaterial used. Examples of pillaring and pillared clays are found in: T.J. Pinnavaia, Science 220 (4595), 365-371 (1983); J. M. Thomas,Intercalation Chemistry, (S. Whittington and A. Jacobson, eds.) Ch. 3,pp. 55-99, Academic Press, Inc., (1972); U.S. Pat. No. 4,452,910; U.S.Pat. No. 5,376,611; and U.S. Pat. No. 4,060,480; the disclosures ofwhich are incorporated herein by reference in their entirety.

The pillaring process can utilize clay minerals having exchangeablecations and layers capable of expanding. Any pillared clay that canenhance the polymerization of olefins in the catalyst composition of thepresent invention can be used. Therefore, suitable clay minerals forpillaring can include, but are not limited to, allophanes; smectites,both dioctahedral (Al) and tri-octahedral (Mg) and derivatives thereofsuch as montmorillonites (bentonites), nontronites, hectorites, orlaponites; halloysites; vermiculites; micas; fluoromicas; chlorites;mixed-layer clays; the fibrous clays including but not limited tosepiolites, attapulgites, and palygorskites; a serpentine clay; illite;laponite; saponite; and any combination thereof. In one aspect, thepillared clay activator-support can comprise bentonite ormontmorillonite. The principal component of bentonite ismontmorillonite.

The pillared clay can be pretreated if desired. For example, a pillaredbentonite can be pretreated by drying at about 300° C. under an inertatmosphere, typically dry nitrogen, for about 3 hours, before beingadded to the polymerization reactor. Although an exemplary pretreatmentis described herein, it should be understood that the preheating can becarried out at many other temperatures and times, including anycombination of temperature and time steps, all of which are encompassedby this invention.

The activator-support used to prepare the catalyst compositions of thepresent invention can be combined with other inorganic supportmaterials, including, but not limited to, zeolites, inorganic oxides,phosphated inorganic oxides, and the like. In one aspect, typicalsupport materials that can be used include, but are not limited to,silica, silica-alumina, alumina, titania, zirconia, magnesia, boria,thoria, aluminophosphate, aluminum phosphate, silica-titania,coprecipitated silica/titania, mixtures thereof, or any combinationthereof.

According to another aspect of the present invention, one or more of thetransition metal complexes can be precontacted with an olefin monomerand an organoaluminum compound for a first period of time prior tocontacting this mixture with the activator-support. Once theprecontacted mixture of the transition metal complex(es), olefinmonomer, and organoaluminum compound is contacted with theactivator-support, the composition further comprising theactivator-support is termed a “postcontacted” mixture. The postcontactedmixture can be allowed to remain in further contact for a second periodof time prior to being charged into the reactor in which thepolymerization process will be carried out.

According to yet another aspect of the present invention, one or more ofthe transition metal complexes can be precontacted with an olefinmonomer and an activator-support for a first period of time prior tocontacting this mixture with the organoaluminum compound. Once theprecontacted mixture of the transition metal complex(es), olefinmonomer, and activator-support is contacted with the organoaluminumcompound, the composition further comprising the organoaluminum istermed a “postcontacted” mixture. The postcontacted mixture can beallowed to remain in further contact for a second period of time priorto being introduced into the polymerization reactor.

Co-Catalysts

In certain aspects directed to catalyst compositions containing aco-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound,examples of which include non-halide metal hydrocarbyl compounds, metalhydrocarbyl halide compounds, non-halide metal alkyl compounds, metalalkyl halide compounds, and so forth. The hydrocarbyl group (or alkylgroup) can be any hydrocarbyl (or alkyl) group disclosed herein.Moreover, in some aspects, the metal of the metal hydrocarbyl can be agroup 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14metal; or alternatively, a group 13 metal. Hence, in some aspects, themetal of the metal hydrocarbyl (non-halide metal hydrocarbyl or metalhydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium,beryllium, magnesium, calcium, strontium, barium, cadmium, boron,aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium,calcium, boron, aluminum, or tin; alternatively, lithium, sodium, orpotassium; alternatively, magnesium or calcium; alternatively, lithium;alternatively, sodium; alternatively, potassium; alternatively,magnesium; alternatively, calcium; alternatively, boron; alternatively,aluminum; or alternatively, tin. In some aspects, the metal hydrocarbylor metal alkyl, with or without a halide, can comprise a lithiumhydrocarbyl or alkyl, a magnesium hydrocarbyl or alkyl, a boronhydrocarbyl or alkyl, or an aluminum hydrocarbyl or alkyl.

In particular aspects directed to catalyst compositions containing anactivator-support and a co-catalyst, the co-catalyst can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organomagnesiumcompound, or an organolithium compound, and this includes anycombinations of these materials. In one aspect, the co-catalyst cancomprise an organoaluminum compound. In another aspect, the co-catalystcan comprise an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, an organomagnesium compound, anorganolithium compound, or any combination thereof. In yet anotheraspect, the co-catalyst can comprise an aluminoxane compound;alternatively, an organoboron or organoborate compound; alternatively,an ionizing ionic compound; alternatively, an organomagnesium compound;or alternatively, an organolithium compound.

Organoaluminum Compounds

In some aspects, catalyst compositions of the present invention cancomprise one or more organoaluminum compounds. Such compounds caninclude, but are not limited to, compounds having the formula:

(R^(X))₃Al;

where R^(X) can be an aliphatic group having from 1 to 10 carbon atoms.For example, R^(X) can be methyl, ethyl, propyl, butyl, hexyl, orisobutyl.

Other organoaluminum compounds which can be used in catalystcompositions disclosed herein can include, but are not limited to,compounds having the formula:

Al(X⁵)_(m)(X⁶)_(3−m).

Generally, the selections of X⁵, X⁶, and m in this formula areindependently described herein, and these selections can be combined inany combination to further describe the organoaluminum compound. In someaspects, m can be from 1 to 3, inclusive, X⁵ can be a C₁ to C₁₈hydrocarbyl group, and X⁶ can be H, a halide, or a C₁ to C₁₈hydrocarboxy group. It is contemplated that each X⁵ (and/or X⁶) can bethe same, or that each X⁵ (and/or X⁶) can be different.

The C₁ to C₁₈ hydrocarbyl and C₁ to C₁₈ hydrocarboxy groups can be anyC₁ to C₁₈ hydrocarbyl and C₁ to C₁₈ hydrocarboxy group disclosed herein.For instance, the C₁ to C₁₈ hydrocarbyl group can be any C₁ to C₁₈ alkylgroup, C₂ to C₁₈ alkenyl group, C₆ to C₁₈ aryl group, or C₇ to C₁₈aralkyl group disclosed herein. Non-limiting examples of suitablehydrocarbyl groups can include, but are not limited to, methyl, ethyl,propyl (e.g., n-propyl), butyl (e.g., n-butyl, isobutyl), pentyl (e.g.,neopentyl), hexyl (e.g., n-hexyl), heptyl, octyl, nonyl, decyl, ethenyl,propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl,decenyl, phenyl, benzyl, or tolyl, and the like. Likewise, non-limitingexamples of suitable hydrocarboxy groups can include, but are notlimited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, phenoxy, toloxy,xyloxy, or benzoxy, and the like.

In one aspect of the present invention, X⁵ can be a C₁ to C₁₈hydrocarbyl group. In another aspect, X⁵ can be a C₁ to C₁₈ alkyl group,or a C₁ to C₁₀ alkyl group. For example, X⁵ can be methyl, ethyl,propyl, n-butyl, sec-butyl, isobutyl, or hexyl, and the like, in yetanother aspect.

According to another aspect of the present invention, X⁶ can be H, ahalide, or a C₁ to C₁₈ hydrocarboxy group. In yet another aspect, X⁶ canbe H, F, or Cl; alternatively, X⁶ can be H; alternatively, X⁶ can be F;or alternatively, X⁶ can be Cl.

In the formula, Al(X⁵)_(m)(X⁶)_(3−m) can be a number from 1 to 3,inclusive, and in some aspects, m can be 3. The value of m is notrestricted to be an integer; therefore, this formula can includesesquihalide compounds or other organoaluminum cluster compounds.

Non-limiting examples of organoaluminum compounds suitable for use inaccordance with the present invention can include, but are not limitedto, trialkylaluminum compounds, dialkylaluminum halide compounds,dialkylaluminum alkoxide compounds, dialkylaluminum hydride compounds,and combinations thereof. Specific non-limiting examples of suitableorganoaluminum compounds can include, but are not limited to,trimethylaluminum (TMA), triethylaluminum (TEA), tri-n-propylaluminum(TNPA), tri-n-butylaluminum (TNBA), triisobutylaluminum (TIBA),tri-n-hexylaluminum, tri-n-octylaluminum, diisobutylaluminum hydride,diethylaluminum ethoxide, diethylaluminum chloride, and the like, orcombinations thereof.

The present invention contemplates a method of precontacting atransition metal complex with an organoaluminum compound and an olefinmonomer to form a precontacted mixture, prior to contacting thisprecontacted mixture with an activator-support to form a catalystcomposition. When the catalyst composition is prepared in this manner,typically, though not necessarily, a portion of the organoaluminumcompound can be added to the precontacted mixture and another portion ofthe organoaluminum compound can be added to the postcontacted mixtureprepared when the precontacted mixture is contacted with the solid oxideactivator-support. However, the entire organoaluminum compound can beused to prepare the catalyst composition in either the precontacting orpostcontacting step. Alternatively, all the catalyst components can becontacted in a single step.

Further, more than one organoaluminum compound can be used in either theprecontacting or the postcontacting step. When an organoaluminumcompound is added in multiple steps, the amounts of organoaluminumcompound disclosed herein include the total amount of organoaluminumcompound used in both the precontacted and postcontacted mixtures, andany additional organoaluminum compound added to the polymerizationreactor. Therefore, total amounts of organoaluminum compounds aredisclosed regardless of whether a single organoaluminum compound or morethan one organoaluminum compound is used.

Aluminoxane Compounds

Certain aspects of the present invention provide a catalyst compositionwhich can comprise an aluminoxane compound. As used herein, the term“aluminoxane” refers to aluminoxane compounds, compositions, mixtures,or discrete species, regardless of how such aluminoxanes are prepared,formed or otherwise provided. For example, a catalyst compositioncomprising an aluminoxane compound can be prepared in which aluminoxaneis provided as the poly(hydrocarbyl aluminum oxide), or in whichaluminoxane is provided as the combination of an aluminum alkyl compoundand a source of active protons such as water. Aluminoxanes also can bereferred to as poly(hydrocarbyl aluminum oxides) or organoaluminoxanes.

The other catalyst components typically can be contacted with thealuminoxane in a saturated hydrocarbon compound solvent, though anysolvent that is substantially inert to the reactants, intermediates, andproducts of the activation step can be used. The catalyst compositionformed in this manner can be collected by any suitable method, forexample, by filtration. Alternatively, the catalyst composition can beintroduced into the polymerization reactor without being isolated.

The aluminoxane compound of this invention can be an oligomeric aluminumcompound comprising linear structures, cyclic structures, or cagestructures, or mixtures of all three. Cyclic aluminoxane compoundshaving the formula:

wherein R in this formula can be a linear or branched alkyl having from1 to 10 carbon atoms, and p in this formula can be an integer from 3 to20, are encompassed by this invention. The AlRO moiety shown here alsocan constitute the repeating unit in a linear aluminoxane. Thus, linearaluminoxanes having the formula:

wherein R in this formula can be a linear or branched alkyl having from1 to 10 carbon atoms, and q in this formula can be an integer from 1 to50, are also encompassed by this invention.

Further, aluminoxanes can have cage structures of the formula R^(t)_(5r+α)R^(b) _(r−α)Al_(4r)O_(3r), wherein R^(t) can be a terminal linearor branched alkyl group having from 1 to 10 carbon atoms; R^(b) can be abridging linear or branched alkyl group having from 1 to 10 carbonatoms; r can be 3 or 4; and a can be equal ton_(Al(3))−n_(O(2))+n_(O(4)), wherein n_(Al(3)) is the number of threecoordinate aluminum atoms, n_(O(2)) is the number of two coordinateoxygen atoms, and n_(O(4)) is the number of 4 coordinate oxygen atoms.

Thus, aluminoxanes which can be employed in the catalyst compositions ofthe present invention can be represented generally by formulas such as(R—Al—O)_(p), R(R—Al—O)_(q)AlR₂, and the like. In these formulas, the Rgroup typically can be a linear or branched C₁-C₆ alkyl, such as methyl,ethyl, propyl, butyl, pentyl, or hexyl. Examples of aluminoxanecompounds that can be used in accordance with the present invention caninclude, but are not limited to, methylaluminoxane, ethylaluminoxane,n-propylaluminoxane, iso-propyl-aluminoxane, n-butylaluminoxane,t-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,isopentylaluminoxane, neopentylaluminoxane, and the like, or anycombination thereof. Methylaluminoxane, ethylaluminoxane, andiso-butylaluminoxane can be prepared from trimethylaluminum,triethylaluminum, or triisobutylaluminum, respectively, and sometimesare referred to as poly(methyl aluminum oxide), poly(ethyl aluminumoxide), and poly(isobutyl aluminum oxide), respectively. It is alsowithin the scope of the invention to use an aluminoxane in combinationwith a trialkylaluminum, such as that disclosed in U.S. Pat. No.4,794,096, incorporated herein by reference in its entirety.

The present invention contemplates many values of p and q in thealuminoxane formulas (R—Al—O)_(p) and R(R—Al—O)_(q)AlR₂, respectively.In some aspects, p and q can be at least 3. However, depending upon howthe organoaluminoxane is prepared, stored, and used, the value of p andq can vary within a single sample of aluminoxane, and such combinationsof organoaluminoxanes are contemplated herein.

In preparing a catalyst composition containing an aluminoxane, the molarratio of the total moles of aluminum in the aluminoxane (oraluminoxanes) to the total moles of transition metal complex(es) in thecomposition generally can be between about 1:10 and about 100,000:1. Inanother aspect, the molar ratio can be in a range from about 5:1 toabout 15,000:1. Optionally, aluminoxane can be added to a polymerizationzone in ranges from about 0.01 mg/L to about 1000 mg/L, from about 0.1mg/L to about 100 mg/L, or from about 1 mg/L to about 50 mg/L.

Organoaluminoxanes can be prepared by various procedures. Examples oforganoaluminoxane preparations are disclosed in U.S. Pat. Nos. 3,242,099and 4,808,561, the disclosures of which are incorporated herein byreference in their entirety. For example, water in an inert organicsolvent can be reacted with an aluminum alkyl compound, such as(R^(X))₃Al, to form the desired organoaluminoxane compound. While notintending to be bound by this statement, it is believed that thissynthetic method can afford a mixture of both linear and cyclic R—Al—Oaluminoxane species, both of which are encompassed by this invention.Alternatively, organoaluminoxanes can be prepared by reacting analuminum alkyl compound, such as (R^(X))₃Al, with a hydrated salt, suchas hydrated copper sulfate, in an inert organic solvent.

Organoboron & Organoborate Compounds

According to another aspect of the present invention, the catalystcomposition can comprise an organoboron or organoborate compound. Suchcompounds can include neutral boron compounds, borate salts, and thelike, or combinations thereof. For example, fluoroorgano boron compoundsand fluoroorgano borate compounds are contemplated.

Any fluoroorgano boron or fluoroorgano borate compound can be utilizedwith the present invention. Examples of fluoroorgano borate compoundsthat can be used in the present invention can include, but are notlimited to, fluorinated aryl borates such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like, ormixtures thereof. Examples of fluoroorgano boron compounds that can beused as co-catalysts in the present invention can include, but are notlimited to, tris(pentafluorophenyl)boron,tris[3,5-bis(trifluoromethyl)-phenyl]boron, and the like, or mixturesthereof. Although not intending to be bound by the following theory,these examples of fluoroorgano borate and fluoroorgano boron compounds,and related compounds, may form “weakly-coordinating” anions whencombined with a transition metal complex (see e.g., U.S. Pat. No.5,919,983, the disclosure of which is incorporated herein by referencein its entirety). Applicants also contemplate the use of diboron, orbis-boron, compounds or other bifunctional compounds containing two ormore boron atoms in the chemical structure, such as disclosed in J. Am.Chem. Soc., 2005, 127, pp. 14756-14768, the content of which isincorporated herein by reference in its entirety.

Generally, any amount of organoboron compound can be used. According toone aspect of this invention, the molar ratio of the total moles oforganoboron or organoborate compound (or compounds) to the total molesof transition metal complex (or complexes) in the catalyst compositioncan be in a range from about 0.1:1 to about 15:1. Typically, the amountof the fluoroorgano boron or fluoroorgano borate compound used can befrom about 0.5 moles to about 10 moles of boron/borate compound per moleof transition metal complex(es). According to another aspect of thisinvention, the amount of fluoroorgano boron or fluoroorgano boratecompound can be from about 0.8 moles to about 5 moles of boron/boratecompound per mole of transition metal complex(es).

Ionizing Ionic Compounds

In another aspect, catalyst compositions disclosed herein can comprisean ionizing ionic compound. An ionizing ionic compound is an ioniccompound that can function as an activator or co-catalyst to enhance theactivity of the catalyst composition. While not intending to be bound bytheory, it is believed that the ionizing ionic compound may be capableof reacting with a transition metal complex and converting thetransition metal complex into one or more cationic transition metalcomplexes, or incipient cationic transition metal complexes. Again,while not intending to be bound by theory, it is believed that theionizing ionic compound can function as an ionizing compound bycompletely or partially extracting an anionic ligand, such as X¹ or X²,from a transition metal complex. However, the ionizing ionic compoundcan be an activator or co-catalyst regardless of whether it is ionizesthe transition metal complex, abstracts a X¹ or X² ligand in a fashionas to form an ion pair, weakens the metal-X¹ or metal-X² bond in thetransition metal complex, simply coordinates to a X¹ or X² ligand, oractivates the transition metal complex by some other mechanism.

Further, it is not necessary that the ionizing ionic compound activatethe transition metal complex only. The activation function of theionizing ionic compound can be evident in the enhanced activity ofcatalyst composition as a whole, as compared to a catalyst compositionthat does not contain an ionizing ionic compound.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl) borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoro-borate,lithium tetrakis(pentafluorophenyl)aluminate, lithiumtetraphenylaluminate, lithium tetrakis(p-tolyl)aluminate, lithiumtetrakis(m-tolyl)aluminate, lithiumtetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,and the like, or combinations thereof. Ionizing ionic compounds usefulin this invention are not limited to these; other examples of ionizingionic compounds are disclosed in U.S. Pat. Nos. 5,576,259 and 5,807,938,the disclosures of which are incorporated herein by reference in theirentirety.

Organomagnesium & Organolithium Compounds

Other aspects are directed to catalyst compositions which can include anorganomagnesium compound, an organolithium compound, or a combinationthereof. In some aspects, the organomagnesium compound and organolithiumcompound compounds can have the following general formulas:

Mg(X¹²)(X¹³); and

Li(X¹⁴).

In these formulas, X¹² and X¹⁴ independently can be a C₁ to C₁₈hydrocarbyl group, and X¹³ can be H, a halide, or a C₁ to C₁₈hydrocarbyl or C₁ to C₁₈ hydrocarboxy group. It is contemplated X¹² andX¹³ can be the same, or that X¹² and X¹³ can be different.

In one aspect, X¹², X¹³, and X¹⁴ independently can be any C₁ to C₁₈hydrocarbyl group, C₁ to C₁₂ hydrocarbyl group, C₁ to C₈ hydrocarbylgroup, or C₁ to C₅ hydrocarbyl group disclosed herein. In anotheraspect, X¹², X¹³, and X¹⁴ independently can be any C₁ to C₁₈ alkylgroup, C₂ to C₁₈ alkenyl group, C₆ to C₁₈ aryl group, or C₇ to C₁₈aralkyl group disclosed herein; alternatively, any C₁ to C₁₂ alkylgroup, C₂ to C₁₂ alkenyl group, C₆ to C₁₂ aryl group, or C₇ to C₁₂aralkyl group disclosed herein; or alternatively, any C₁ to C₅ alkylgroup, C₂ to C₅ alkenyl group, C₆ to C₈ aryl group, or C₇ to C₈ aralkylgroup disclosed herein. Thus, X¹², X¹³, and X¹⁴ independently can be amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, adecyl group, a undecyl group, a dodecyl group, a tridecyl group, atetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecylgroup, an octadecyl group, an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, a decenyl group, a undecenyl group, a dodecenylgroup, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, ahexadecenyl group, a heptadecenyl group, an octadecenyl group, a phenylgroup, a naphthyl group, a benzyl group, or a tolyl group, and the like.In yet another aspect, X¹², X¹³, and X¹⁴ independently can be methyl,ethyl, propyl, butyl, or pentyl (e.g., neopentyl), or both or both X¹²and X¹³ can be methyl, or ethyl, or propyl, or butyl, or pentyl (e.g.,neopentyl).

X¹³ can be H, a halide, or a C₁ to C₁₈ hydrocarbyl or C₁ to C₁₈hydrocarboxy group (e.g., any C₁ to C₁₈, C₁ to C₁₂, C₁ to C₁₀, or C₁ toC₈ hydrocarboxy group disclosed herein). In some aspects, X¹³ can be H,a halide (e.g., Cl), or a C₁ to C₁₈ hydrocarbyl or C₁ to C₁₈hydrocarboxy group; alternatively, H, a halide, or a C₁ to C₈hydrocarbyl or C₁ to C₈ hydrocarboxy group; or alternatively, H, Br, Cl,F, I, methyl, ethyl, propyl, butyl, pentyl (e.g., neopentyl), hexyl,heptyl, octyl, nonyl, decyl, ethenyl, propenyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, nonenyl, decenyl, phenyl, benzyl, tolyl,methoxy, ethoxy, propoxy, butoxy, pentoxy, phenoxy, toloxy, xyloxy, orbenzoxy.

In other aspects, the organomagnesium compound can have one or twohydrocarbylsilyl moieties. Each hydrocarbyl of the hydrocarbylsilylgroup can be any hydrocarbyl group disclosed herein (e.g., a C₁ to C₁₈alkyl group, a C₂ to C₁₈ alkenyl group, a C₆ to C₁₈ aryl group, a C₇ toC₁₈ aralkyl group, etc.). Illustrative and non-limiting examples ofhydrocarbylsilyl groups can include, but are not limited to,trimethylsilyl, triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl),tributylsilyl, tripentylsilyl, triphenylsilyl, allyldimethylsilyl,trimethylsilylmethyl, and the like.

Exemplary organomagnesium compounds can include, but are not limited to,dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombination thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Catalyst Compositions

The methods disclosed herein are not limited to particulartransition-metal based catalyst systems or compositions, but rather, canbe applied to any transition-metal based catalyst system or compositionsuitable for the polymerization of an olefin monomer (and optionalcomonomer(s)). The transition-metal based catalyst composition cancomprise, for example, a transition metal (one or more than one) fromGroups IIIB-VIIIB of the Periodic Table of the Elements. In one aspect,the transition metal-based catalyst composition can comprise a GroupIII, IV, V, or VI transition metal, or a combination of two or moretransition metals. The transition metal-based catalyst composition cancomprise chromium, titanium, zirconium, hafnium, vanadium, or acombination thereof, in one aspect, or can comprise chromium, titanium,zirconium, hafnium, or a combination thereof, in another aspect.Accordingly, the transition metal-based catalyst system can comprisechromium, or titanium, or zirconium, or hafnium, either singly or incombination.

Various transition metal-based catalyst systems or compositions known toa skilled artisan are useful in the polymerization of olefins. Theseinclude, but are not limited to, Ziegler-Natta based catalystcompositions, chromium-based catalyst compositions, metallocene-basedcatalyst compositions, and the like, including combinations thereof. Themethods disclosed herein are not limited to the aforementioned catalystcompositions, but Applicants nevertheless contemplate particular aspectsdirected to these catalyst compositions. Hence, the transitionmetal-based catalyst composition can be a Ziegler-Natta based catalystcomposition, a chromium-based catalyst composition, and/or ametallocene-based catalyst composition; alternatively, a Ziegler-Nattabased catalyst composition; alternatively, a chromium-based catalystcomposition; or alternatively, a metallocene-based catalyst composition.Examples of representative and non-limiting transition metal-basedcatalysts systems or compositions include those disclosed in the U.S.Pat. Nos. 3,887,494, 3,119,569, 4,053,436, 4,981,831, 4,364,842,4,444,965, 4,364,855, 4,504,638, 4,364,854, 4,444,964, 4,444,962,3,976,632, 4,248,735, 4,297,460, 4,397,766, 2,825,721, 3,225,023,3,226,205, 3,622,521, 3,625,864, 3,900,457, 4,301,034, 4,547,557,4,339,559, 4,806,513, 5,037,911, 5,219,817, 5,221,654, 3,887,494,3,900,457, 4,053,436, 4,081,407, 4,296,001, 4,392,990, 4,405,501,4,981,831, 4,151,122, 4,247,421, 4,248,735, 4,297,460, 4,397,769,4,460,756, 4,182,815, 4,735,931, 4,820,785, 4,988,657, 5,436,305,5,610,247, 5,627,247, 3,242,099, 4,808,561, 5,275,992, 5,237,025,5,244,990, 5,179,178, 4,855,271, 5,179,178, 5,275,992, 3,887,494,3,119,569, 3,900,457, 4,981,831, 4,364,842, 4,444,965, 4,939,217,5,210,352, 5,436,305, 5,401,817, 5,631,335, 5,571,880, 5,191,132,5,480,848, 5,399,636, 5,565,592, 5,347,026, 5,594,078, 5,498,581,5,496,781, 5,563,284, 5,554,795, 5,420,320, 5,451,649, 5,541,272,5,705,478, 5,631,203, 5,654,454, 5,705,579, 5,668,230, 6,300,271,6,831,141, 6,653,416, 6,613,712, 7,294,599, 6,355,594, 6,395,666,6,833,338, 7,417,097, 6,548,442, and 7,312,283, each of which isincorporated herein by reference in its entirety.

In one aspect, the transition metal compound or complex (one or more) inthe catalyst composition can comprise a metallocene compound. A“metallocene” compound contains at least one η³ toη⁵-cyclopentadienyl-type moiety, wherein η³ to η⁵-cycloalkadienylmoieties include cyclopentadienyl ligands, indenyl ligands, fluorenylligands, and the like, including saturated, partially saturated, and/orsubstituted derivatives or analogs of any of these. Possiblesubstituents on these ligands may include hydrogen, therefore thisdescription encompasses ligands such as tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, partially saturated indenyl,partially saturated fluorenyl, substituted partially saturated indenyl,substituted partially saturated fluorenyl, and the like. The metallocenecompound can contain one cyclopentadienyl-type moiety (half-sandwich) ortwo cyclopentadienyl-type moieties (full-sandwich).

Additionally or alternatively, the transition metal compound or complexin the catalyst composition can comprise one or more compoundscontaining chromium, titanium, zirconium, hafnium, and/or vanadium.Thus, the transition metal compound or complex can comprise ametallocene compound containing chromium, titanium, zirconium, hafnium,and/or vanadium, or a non-metallocene compound containing chromium,titanium, zirconium, hafnium, and/or vanadium. In another aspect, thetransition metal compound or complex in the catalyst composition cancomprise a compound containing titanium, zirconium, or hafnium. In yetanother aspect, the transition metal compound or complex in the catalystcomposition can comprise a compound containing chromium. For instance,the transition metal compound or complex in the catalyst composition canhave the formula:

Cr(X^(A))(X¹)(X²)(L)_(n)  (II).

Within formula (II), X^(A), X¹, X², L, and n are independent elements ofthe transition metal compound. Accordingly, the transition metalcompound having formula (II) may be described using any combination ofX^(A), X¹, X², L and n disclosed herein.

Unless otherwise specified, formula (II) above, any other structuralformulas disclosed herein, and any transition metal complex, compound,or species (e.g., a metallocene compound) disclosed herein are notdesigned to show stereochemistry or isomeric positioning of thedifferent moieties (e.g., these formulas are not intended to display cisor trans isomers, or R or S diastereoisomers), although such compoundsare contemplated and encompassed by these formulas and/or structures.

X¹ and X² in formula (II) independently can be a monoanionic ligand. Insome aspects, suitable monoanionic ligands can include, but are notlimited to, H (hydride), a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁to C₃₆ hydrocarboxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ toC₃₆ hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group,—OBR^(A) ₂, or —OSO₂R^(A), wherein R^(A) is a C₁ to C₃₆ hydrocarbylgroup. It is contemplated that X¹ and X² can be either the same or adifferent monoanionic ligand.

In one aspect, X¹ and X² independently can be H, a halide (e.g., F, Cl,Br, etc.), a C₁ to C₁₈ hydrocarbyl group, a C₁ to C₁₈ hydrocarboxygroup, a C₁ to C₁₈ hydrocarbylaminyl group, a C₁ to C₁₈ hydrocarbylsilylgroup, or a C₁ to C₁₈ hydrocarbylaminylsilyl group. Alternatively, X¹and X² independently can be H, a halide, OBR^(A) ₂, or OSO₂R^(A),wherein R^(A) is a C₁ to C₁₈ hydrocarbyl group. In another aspect, X¹and X² independently can be H, a halide, a C₁ to C₁₂ hydrocarbyl group,a C₁ to C₁₂ hydrocarboxy group, a C₁ to C₁₂ hydrocarbylaminyl group, aC₁ to C₁₂ hydrocarbylsilyl group, a C₁ to C₁₂ hydrocarbylaminylsilylgroup, OBR^(A) ₂, or OSO₂R^(A), wherein R^(A) is a C₁ to C₁₂ hydrocarbylgroup. In yet another aspect, X¹ and X² independently can be H, ahalide, a C₁ to C₁₀ hydrocarbyl group, a C₁ to C₁₀ hydrocarboxy group, aC₁ to C₁₀ hydrocarbylaminyl group, a C₁ to C₁₀ hydrocarbylsilyl group, aC₁ to C₁₀ hydrocarbylaminylsilyl group, OBR^(A) ₂, or OSO₂R^(A), whereinR^(A) is a C₁ to C₁₀ hydrocarbyl group. In still another aspect, X¹ andX² independently can be H, a halide, a C₁ to C₈ hydrocarbyl group, a C₁to C₈ hydrocarboxy group, a C₁ to C₈ hydrocarbylaminyl group, a C₁ to C₈hydrocarbylsilyl group, a C₁ to C₈ hydrocarbylaminylsilyl group, OBR^(A)₂, or OSO₂R^(A), wherein R^(A) is a C₁ to C₈ hydrocarbyl group.

The hydrocarbyl group which can be X¹ and/or X² in formula (II) can be aC₁ to C₃₆ hydrocarbyl group, including, but not limited to, a C₁ to C₃₆alkyl group, a C₂ to C₃₆ alkenyl group, a C₄ to C₃₆ cycloalkyl group, aC₆ to C₃₆ aryl group, or a C₇ to C₃₆ aralkyl group. For instance, X¹ andX² independently can be a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenylgroup, a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ toC₁₈ aralkyl group; alternatively, X¹ and X² independently can be a C₁ toC₁₂ alkyl group, a C₂ to C₁₂ alkenyl group, a C₄ to C₁₂ cycloalkylgroup, a C₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group;alternatively, X¹ and X² independently can be a C₁ to C₁₀ alkyl group, aC₂ to C₁₀ alkenyl group, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ arylgroup, or a C₇ to C₁₀ aralkyl group; or alternatively, X¹ and X²independently can be a C₁ to C₅ alkyl group, a C₂ to C₅ alkenyl group, aC₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or a C₇ to C₈ aralkylgroup.

Accordingly, in some aspects, the alkyl group which can be X¹ and/or X²in formula (II) can be a methyl group, an ethyl group, a propyl group, abutyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, a decyl group, a undecyl group, a dodecyl group, atridecyl group, a tetradecyl group, a pentadecyl group, a hexadecylgroup, a heptadecyl group, or an octadecyl group; or alternatively, amethyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, an octyl group, a nonyl group, ora decyl group. In some aspects, the alkyl group which can be X¹ and/orX² in formula (II) can be a methyl group, an ethyl group, a n-propylgroup, an iso-propyl group, a n-butyl group, an iso-butyl group, asec-butyl group, a tert-butyl group, a n-pentyl group, an iso-pentylgroup, a sec-pentyl group, or a neopentyl group; alternatively, a methylgroup, an ethyl group, an iso-propyl group, a tert-butyl group, or aneopentyl group; alternatively, a methyl group; alternatively, an ethylgroup; alternatively, a n-propyl group; alternatively, an iso-propylgroup; alternatively, a tert-butyl group; or alternatively, a neopentylgroup.

Suitable alkenyl groups which can be X¹ and/or X² in formula (II) caninclude, but are not limited to, an ethenyl group, a propenyl group, abutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a undecenyl group, adodecenyl group, a tridecenyl group, a tetradecenyl group, apentadecenyl group, a hexadecenyl group, a heptadecenyl group, or anoctadecenyl group. Such alkenyl groups can be linear or branched, andthe double bond can be located anywhere in the chain. In one aspect, X¹and/or X² in formula (II) can be an ethenyl group, a propenyl group, abutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, or a decenyl group, while in anotheraspect, X¹ and/or X² in formula (II) can be an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, or a hexenyl group. Forexample, X¹ and/or X² can be an ethenyl group; alternatively, a propenylgroup; alternatively, a butenyl group; alternatively, a pentenyl group;or alternatively, a hexenyl group. In yet another aspect, X¹ and/or X²can be a terminal alkenyl group, such as a C₃ to C₁₈ terminal alkenylgroup, a C₃ to C₁₂ terminal alkenyl group, or a C₃ to C₈ terminalalkenyl group. Illustrative terminal alkenyl groups can include, but arenot limited to, a prop-2-en-1-yl group, a bute-3-en-1-yl group, apent-4-en-1-yl group, a hex-5-en-1-yl group, a hept-6-en-1-yl group, anocte-7-en-1-yl group, a non-8-en-1-yl group, a dece-9-en-1-yl group, andso forth.

X¹ and/or X² in formula (II) can be a cycloalkyl group, including, butnot limited to, a cyclobutyl group, a substituted cyclobutyl group, acyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group,a substituted cyclohexyl group, a cycloheptyl group, a substitutedcycloheptyl group, a cyclooctyl group, or a substituted cyclooctylgroup. For example, X¹ and/or X² in formula (II) can be a cyclopentylgroup, a substituted cyclopentyl group, a cyclohexyl group, or asubstituted cyclohexyl group. Moreover, X¹ and/or X² in formula (II) canbe a cyclobutyl group or a substituted cyclobutyl group; alternatively,a cyclopentyl group or a substituted cyclopentyl group; alternatively, acyclohexyl group or a substituted cyclohexyl group; alternatively, acycloheptyl group or a substituted cycloheptyl group; alternatively, acyclooctyl group or a substituted cyclooctyl group; alternatively, acyclopentyl group; alternatively, a substituted cyclopentyl group;alternatively, a cyclohexyl group; or alternatively, a substitutedcyclohexyl group. Substituents which can be utilized for the substitutedcycloalkyl group are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted cycloalkyl groupwhich can be X¹ and/or X² in formula (II).

In some aspects, the aryl group which can be X¹ and/or X² in formula(II) can be a phenyl group, a substituted phenyl group, a naphthylgroup, or a substituted naphthyl group.

In an aspect, the aryl group can be a phenyl group or a substitutedphenyl group; alternatively, a naphthyl group or a substituted naphthylgroup; alternatively, a phenyl group or a naphthyl group; alternatively,a substituted phenyl group or a substituted naphthyl group;alternatively, a phenyl group; or alternatively, a naphthyl group.Substituents which can be utilized for the substituted phenyl groups orsubstituted naphthyl groups are independently disclosed herein and canbe utilized without limitation to further describe the substitutedphenyl groups or substituted naphthyl groups which can be X¹ and/or X²in formula (II).

In an aspect, the substituted phenyl group which can be X¹ and/or X² informula (II) can be a 2-substituted phenyl group, a 3-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other aspects, the substitutedphenyl group can be a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.Substituents which can be utilized for these specific substituted phenylgroups are independently disclosed herein and can be utilized withoutlimitation to further describe these substituted phenyl groups which canbe the X¹ and/or X² group(s) in formula (II).

In some aspects, the aralkyl group which can be X¹ and/or X² group informula (II) can be a benzyl group or a substituted benzyl group. In anaspect, the aralkyl group can be a benzyl group or, alternatively, asubstituted benzyl group. Substituents which can be utilized for thesubstituted aralkyl group are independently disclosed herein and can beutilized without limitation to further describe the substituted aralkylgroup which can be the X¹ and/or X² group(s) in formula (II).

In an aspect, each non-hydrogen substituent(s) for the substitutedcycloalkyl group, substituted aryl group, or substituted aralkyl groupwhich can be X¹ and/or X² in formula (II) independently can be a C₁ toC₁₈ hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group. Specific hydrocarbyl groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents of the substitutedcycloalkyl groups, substituted aryl groups, or substituted aralkylgroups which can be X¹ and/or X² in formula (II). For instance, thehydrocarbyl substituent can be an alkyl group, such as a methyl group,an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, an isobutyl group, a tert-butyl group, a n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group, and the like. Furthermore, the hydrocarbylsubstituent can be a benzyl group, a phenyl group, a tolyl group, or axylyl group, and the like.

A hydrocarboxy group is used generically herein to include, forinstance, alkoxy, aryloxy, aralkoxy, and -(alkyl, aryl, oraralkyl)-O-(alkyl, aryl, or aralkyl) groups, and such groups which aresuitable for X¹ and/or X² can comprise up to about 36 carbon atoms(e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarboxygroups). Illustrative and non-limiting examples of hydrocarboxy groupswhich can be X¹ and/or X² in formula (II) can include, but are notlimited to, a methoxy group, an ethoxy group, an n-propoxy group, anisopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxygroup, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, a neo-pentoxy group,a phenoxy group, a toloxy group, a xyloxy group, a2,4,6-trimethylphenoxy group, a benzoxy group, an acetylacetonate group(acac), and the like. In an aspect, the hydrocarboxy group which can beX¹ and/or X² in formula (II) can be a methoxy group; alternatively, anethoxy group; alternatively, an n-propoxy group; alternatively, anisopropoxy group; alternatively, an n-butoxy group; alternatively, asec-butoxy group; alternatively, an isobutoxy group; alternatively, atert-butoxy group; alternatively, an n-pentoxy group; alternatively, a2-pentoxy group; alternatively, a 3-pentoxy group; alternatively, a2-methyl-1-butoxy group; alternatively, a tert-pentoxy group;alternatively, a 3-methyl-1-butoxy group, alternatively, a3-methyl-2-butoxy group; alternatively, a neo-pentoxy group;alternatively, a phenoxy group; alternatively, a toloxy group;alternatively, a xyloxy group; alternatively, a 2,4,6-trimethylphenoxygroup; alternatively, a benzoxy group; or alternatively, anacetylacetonate group.

The term hydrocarbylaminyl group is used generically herein to refercollectively to, for instance, alkylaminyl, arylaminyl, aralkylaminyl,dialkylaminyl, diarylaminyl, diaralkylaminyl, and -(alkyl, aryl, oraralkyl)-N-(alkyl, aryl, or aralkyl) groups, and unless otherwisespecified, the hydrocarbylaminyl groups which can be X¹ and/or X² informula (II) can comprise up to about 36 carbon atoms (e.g., C₁ to C₃₆,C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarbylaminyl groups).Accordingly, hydrocarbylaminyl is intended to cover both(mono)hydrocarbylaminyl and dihydrocarbylaminyl groups. In some aspects,the hydrocarbylaminyl group which can be X¹ and/or X² in formula (II)can be, for instance, a methylaminyl group (—NHCH₃), an ethylaminylgroup (—NHCH₂CH₃), an n-propylaminyl group (—NHCH₂CH₂CH₃), aniso-propylaminyl group (—NHCH(CH₃)₂), an n-butylaminyl group(—NHCH₂CH₂CH₂CH₃), a t-butylaminyl group (—NHC(CH₃)₃), an n-pentylaminylgroup (—NHCH₂CH₂CH₂CH₂CH₃), a neo-pentylaminyl group (—NHCH₂C(CH₃)₃), aphenylaminyl group (—NHC₆H₅), a tolylaminyl group (—NHC₆H₄—CH₃), or axylylaminyl group (—NHC₆H₃(CH₃)₂); alternatively, a methylaminyl group;alternatively, an ethylaminyl group; alternatively, a propylaminylgroup; or alternatively, a phenylaminyl group. In other aspects, thehydrocarbylaminyl group which can be X¹ and/or X² in formula (II) canbe, for instance, a dimethylaminyl group (—N(CH₃)₂), a diethylaminylgroup (—N(CH₂CH₃)₂), a di-n-propylaminyl group (—N(CH₂CH₂CH₃)₂), adi-iso-propylaminyl group (—N(CH(CH₃)₂)₂), a di-n-butylaminyl group(—N(CH₂CH₂CH₂CH₃)₂), a di-t-butylaminyl group (—N(C(CH₃)₃)₂), adi-n-pentylaminyl group (—N(CH₂CH₂CH₂CH₂CH₃)₂), a di-neo-pentylaminylgroup (—N(CH₂C(CH₃)₃)₂), a di-phenylaminyl group (—N(C₆H₅)₂), adi-tolylaminyl group (—N(C₆H₄—CH₃)₂), or a di-xylylaminyl group(—N(C₆H₃(CH₃)₂)₂); alternatively, a dimethylaminyl group; alternatively,a di-ethylaminyl group; alternatively, a di-n-propylaminyl group; oralternatively, a di-phenylaminyl group.

In accordance with some aspects disclosed herein, one or both of X¹ andX² independently can be a C₁ to C₃₆ hydrocarbylsilyl group;alternatively, a C₁ to C₂₄ hydrocarbylsilyl group; alternatively, a C₁to C₁₈ hydrocarbylsilyl group; or alternatively, a C₁ to C₈hydrocarbylsilyl group. In an aspect, each hydrocarbyl (one or more) ofthe hydrocarbylsilyl group can be any hydrocarbyl group disclosed herein(e.g., a C₁ to C₅ alkyl group, a C₂ to C₅ alkenyl group, a C₅ to C₈cycloalkyl group, a C₆ to C₈ aryl group, a C₇ to C₈ aralkyl group,etc.). As used herein, hydrocarbylsilyl is intended to cover(mono)hydrocarbylsilyl (—SiH₂R), dihydrocarbylsilyl (—SiHR₂), andtrihydrocarbylsilyl (—SiR₃) groups, with R being a hydrocarbyl group. Inone aspect, the hydrocarbylsilyl group can be a C₃ to C₃₆ or a C₃ to C₁₈trihydrocarbylsilyl group, such as, for example, a trialkylsilyl groupor a triphenylsilyl group. Illustrative and non-limiting examples ofhydrocarbylsilyl groups which can be the X¹ and/or X² group(s) informula (II) can include, but are not limited to, trimethylsilyl,triethylsilyl, tripropylsilyl (e.g., triisopropylsilyl), tributylsilyl,tripentylsilyl, triphenylsilyl, allyldimethylsilyl, and the like.

A hydrocarbylaminylsilyl group is used herein to refer to groupscontaining at least one hydrocarbon moiety, at least one N atom, and atleast one Si atom. Illustrative and non-limiting examples ofhydrocarbylaminylsilyl groups which can be X¹ and/or X² can include, butare not limited to —N(SiMe₃)₂, —N(SiEt₃)₂, and the like. Unlessotherwise specified, the hydrocarbylaminylsilyl groups which can be X¹and/or X² can comprise up to about 36 carbon atoms (e.g., C₁ to C₃₆, C₁to C₁₈, C₁ to C₁₂, or C₁ to C₈ hydrocarbylaminylsilyl groups). In anaspect, each hydrocarbyl (one or more) of the hydrocarbylaminylsilylgroup can be any hydrocarbyl group disclosed herein (e.g., a C₁ to C₅alkyl group, a C₂ to C₅ alkenyl group, a C₅ to C₈ cycloalkyl group, a C₆to C₈ aryl group, a C₇ to C₈ aralkyl group, etc.). Moreover,hydrocarbylaminylsilyl is intended to cover —NH(SiH₂R), —NH(SiHR₂),—NH(SiR₃), —N(SiH₂R)₂, —N(SiHR₂)₂, —N(SiR₃)₂, groups, among others, withR being a hydrocarbyl group.

In an aspect, X¹ and X² independently can be —OBR^(A) ₂ or —OSO₂R^(A),wherein R^(A) is a C₁ to C₃₆ hydrocarbyl group, or alternatively, a C₁to C₁₈ hydrocarbyl group. The hydrocarbyl group in OBR^(A) ₂ and/orOSO₂R^(A) independently can be any hydrocarbyl group disclosed herein,such as, for instance, a C₁ to C₁₈ alkyl group, a C₂ to C₁₈ alkenylgroup, a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, or a C₇ toC₁₈ aralkyl group; a C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenyl group, aC₄ to C₁₂ cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ to C₁₂aralkyl group; or a C₁ to C₈ alkyl group, a C₂ to C₈ alkenyl group, a C₅to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or a C₇ to C₈ aralkylgroup.

In one aspect, X¹ and X² independently can be H, a halide, or a C₁ toC₃₆ hydrocarbyl group, hydrocarboxy group, hydrocarbylaminyl group,hydrocarbylsilyl group, or hydrocarbylaminylsilyl group, while inanother aspect, X¹ and X² independently can be H, or a C₁ to C₁₈hydrocarboxy group, hydrocarbylaminyl group, hydrocarbylsilyl group, orhydrocarbylaminylsilyl group. In yet another aspect, X¹ and X²independently can be a halide; alternatively, a C₁ to C₁₈ hydrocarbylgroup; alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, aC₁ to C₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₁₈hydrocarbylaminylsilyl group. In still another aspect, both X¹ and X²can be H; alternatively, F; alternatively, Cl; alternatively, Br;alternatively, I; alternatively, a C₁ to C₁₈ hydrocarbyl group;alternatively, a C₁ to C₁₈ hydrocarboxy group; alternatively, a C₁ toC₁₈ hydrocarbylaminyl group; alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup; or alternatively, a C₁ to C₁₈ hydrocarbylaminylsilyl group.

X¹ and X² independently can be, in some aspects, H, a halide, methyl,phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, an alkylaminyl,a dialkylaminyl, a trihydrocarbylsilyl, or a hydrocarbylaminylsilyl;alternatively, H, a halide, methyl, phenyl, or benzyl; alternatively, analkoxy, an aryloxy, or acetylacetonate; alternatively, an alkylaminyl ora dialkylaminyl; alternatively, a trihydrocarbylsilyl orhydrocarbylaminylsilyl; alternatively, H or a halide; alternatively,methyl, phenyl, benzyl, an alkoxy, an aryloxy, acetylacetonate, analkylaminyl, or a dialkylaminyl; alternatively, H; alternatively, ahalide; alternatively, methyl; alternatively, phenyl; alternatively,benzyl; alternatively, an alkoxy; alternatively, an aryloxy;alternatively, acetylacetonate; alternatively, an alkylaminyl;alternatively, a dialkylaminyl; alternatively, a trihydrocarbylsilyl; oralternatively, a hydrocarbylaminylsilyl. In these and other aspects, thealkoxy, aryloxy, alkylaminyl, dialkylaminyl, trihydrocarbylsilyl, andhydrocarbylaminylsilyl can be a C₁ to C₃₆, a C₁ to C₁₈, a C₁ to C₁₂, ora C₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, and hydrocarbylaminylsilyl.

Moreover, X¹ and X² independently can be, in certain aspects, a halideor a C₁ to C₁₈ hydrocarbyl group; alternatively, a halide or a C₁ to C₈hydrocarbyl group; alternatively, F, Cl, Br, I, methyl, benzyl, orphenyl; alternatively, Cl, methyl, benzyl, or phenyl; alternatively, aC₁ to C₁₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; alternatively, aC₁ to C₈ alkoxy, aryloxy, alkylaminyl, dialkylaminyl,trihydrocarbylsilyl, or hydrocarbylaminylsilyl group; or alternatively,methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl,decyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl,nonenyl, decenyl, phenyl, tolyl, benzyl, naphthyl, trimethylsilyl,triisopropylsilyl, triphenylsilyl, or allyldimethylsilyl.

In formula (II), X^(A) can be a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group. In one aspect, X^(A) canbe an unsubstituted cyclopentadienyl, indenyl, or fluorenyl group;alternatively, an unsubstituted cyclopentadienyl group; alternatively,an unsubstituted indenyl group; or alternatively, an unsubstitutedfluorenyl group. In another aspect, X^(A) can be a substitutedcyclopentadienyl, indenyl, or fluorenyl group; alternatively, asubstituted cyclopentadienyl group; alternatively, a substituted indenylgroup; or alternatively, a substituted fluorenyl group. Any substituenton the substituted cyclopentadienyl, indenyl, or fluorenyl groupindependently can be H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ toC₃₆ halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or aC₁ to C₃₆ hydrocarbylsilyl group. Since possible substituents on thesesubstituted cyclopentadienyl, indenyl, and fluorenyl groups can includehydrogen, ligands such as tetrahydroindenyl, tetrahydrofluorenyl,octahydrofluorenyl, partially saturated indenyl, partially saturatedfluorenyl, substituted partially saturated indenyl, substitutedpartially saturated fluorenyl, and the like, are encompassed herein.

In some aspects, each substituent independently can be H; alternatively,a halide; alternatively, a C₁ to C₁₈ hydrocarbyl group; alternatively, aC₁ to C₁₈ halogenated hydrocarbyl group; alternatively, a C₁ to C₁₈hydrocarboxy group; or alternatively, a C₁ to C₁₈ hydrocarbylsilylgroup. Importantly, each X^(A) can be either the same or a differentsubstituent group. Moreover, each X^(A) can be at any position(s) of therespective cyclopentadienyl, indenyl, or fluorenyl ring structure thatconforms with the rules of chemical valence.

The halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group,and C₁ to C₃₆ hydrocarbylsilyl group which can be a substituent on thesubstituted cyclopentadienyl, indenyl, or fluorenyl group can be anyhalide, C₁ to C₃₆ hydrocarbyl group, C₁ toC_(36 hydrocarboxy group, and C) ₁ to C₃₆ hydrocarbylsilyl groupdescribed herein (e.g., as pertaining to X¹ and X² in formula (II)).Each substituent on the substituted cyclopentadienyl, indenyl, orfluorenyl group in formula (II) can be, in certain aspects, a C₁ to C₃₆halogenated hydrocarbyl group, where the halogenated hydrocarbyl groupindicates the presence of one or more halogen atoms replacing anequivalent number of hydrogen atoms in the hydrocarbyl group. Thehalogenated hydrocarbyl group often can be a halogenated alkyl group, ahalogenated alkenyl group, a halogenated cycloalkyl group, a halogenatedaryl group, or a halogenated aralkyl group. Representative andnon-limiting halogenated hydrocarbyl groups include pentafluorophenyl,trifluoromethyl (CF₃), and the like.

As a non-limiting example, each substituent on the substitutedcyclopentadienyl, indenyl, or fluorenyl group in formula (II)independently can be H, C₁, CF₃, a methyl group, an ethyl group, apropyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group,a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group, a benzyl group, a naphthyl group,a trimethylsilyl group, a triisopropylsilyl group, a triphenylsilylgroup, or an allyldimethylsilyl group; alternatively, H; alternatively,Cl; alternatively, CF₃; alternatively, a methyl group; alternatively, anethyl group; alternatively, a propyl group; alternatively, a butylgroup; alternatively, a pentyl group; alternatively, a hexyl group;alternatively, a heptyl group; alternatively, an octyl group;alternatively, a nonyl group; alternatively, a decyl group;alternatively, an ethenyl group; alternatively, a propenyl group;alternatively, a butenyl group; alternatively, a pentenyl group;alternatively, a hexenyl group; alternatively, a heptenyl group;alternatively, an octenyl group; alternatively, a nonenyl group;alternatively, a decenyl group; alternatively, a phenyl group;alternatively, a tolyl group; alternatively, a benzyl group;alternatively, a naphthyl group; alternatively, a trimethylsilyl group;alternatively, a triisopropylsilyl group; alternatively, atriphenylsilyl group; or alternatively, an allyldimethylsilyl group.

If X^(A) is a substituted cyclopentadienyl, indenyl, or fluorenyl group,it may have one substituent, 2 substituents, 3 substituents, 4substituents, 5 substituents, etc., each of which independently can beany halide, any C₁ to C₃₆ hydrocarbyl group, any C₁ to C₃₆ halogenatedhydrocarbyl group, any C₁ to C₃₆ hydrocarboxy group, or any C₁ to C₃₆hydrocarbylsilyl group disclosed herein. Moreover, hydrogen also can bea substituent, resulting in partially or fully saturated ligands. Forexample, X^(A) can be a mono-substituted cyclopentadienyl, indenyl, orfluorenyl group, or a di-substituted cyclopentadienyl, indenyl, orfluorenyl group, and each substituent independently can be H, C₁, CF₃, amethyl group, an ethyl group, a propyl group, a butyl group (e.g.,t-Bu), a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, a decyl group, an ethenyl group, a propenyl group, abutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, a tolylgroup, a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group. In another non-limiting example, X^(A) can bea cyclopentadienyl, indenyl, or fluorenyl group, with 5 substituents,such as a pentamethylcyclopentadienyl group.

Each L in formula (II) independently can be neutral ligand, and theinteger n in formula (II) can be 0, 1 or 2 (e.g., n can be 0 or 1). Inan aspect, suitable neutral ligands can include sigma-donor solventsthat contain a coordinating atom (or atoms) that can coordinate to thetransition metal atom in formula (II). Examples of suitable coordinatingatoms in the neutral ligands can include, but are not limited to, O, N,S, and P, or combinations of these atoms. Unless otherwise specified,the neutral ligand can be unsubstituted or can be substituted.Substituent groups are independently described herein and can beutilized, without limitation to further describe a neutral ligand whichcan be utilized as L in formula (II). In some aspects, the neutralligand can be a Lewis base. When the integer n is equal to 2, it iscontemplated that the two neutral ligands can be either the same ordifferent.

In an aspect, each neutral ligand, L, independently can be an ether, athioether, an amine, a nitrile, or a phosphine. In another aspect, eachneutral ligand independently can be an acyclic ether, a cyclic ether, anacyclic thioether, a cyclic thioether, a nitrile, an acyclic amine, acyclic amine, an acyclic phosphine, or a cyclic phosphine. In otheraspects, each neutral ligand independently can be an acyclic ether or acyclic ether; alternatively, an acyclic thioether or a cyclic thioether;alternatively, an acyclic amine or a cyclic amine; alternatively, anacyclic phosphine or a cyclic phosphine; alternatively, an acyclicether; alternatively, a cyclic ether; alternatively, an acyclicthioether; alternatively, a cyclic thioether; alternatively, a nitrile;alternatively, an acyclic amine; alternatively, a cyclic amine;alternatively, an acyclic phosphine; or alternatively, a cyclicphosphine. Further, each neutral ligand independently can include anysubstituted analogs of any acyclic ether, cyclic ether, acyclicthioether, cyclic thioether, nitrile, acyclic amine, cyclic amine,acyclic phosphine, or cyclic phosphine, as disclosed herein.

In an aspect, each neutral ligand independently can be a nitrile havingthe formula R¹C≡N, an ether having the formula R²—O—R³, a thioetherhaving the formula R⁴—S—R⁵, an amine having the formula NR⁶R⁷R⁸, NHR⁶R⁷,or NH₂R⁶, or a phosphine having the formula PR⁹R¹⁰R¹¹, PHR⁹R¹⁰, orPH₂R⁹; alternatively, a nitrile having the formula R¹C≡N, an etherhaving the formula R²—O—R³, a thioether having the formula R⁴—S—R⁵, anamine having the formula NR⁶R⁷R⁸, or a phosphine having the formulaPR⁹R¹⁰R¹¹; or alternatively, a nitrile having the formula R¹C≡N, anether having the formula R²—O—R³, a thioether having the formulaR⁴—S—R⁵, an amine having the formula NR⁶R⁷R⁸, or a phosphine having theformula PR⁹R¹⁰R¹¹. In an aspect, each neutral ligand independently canbe a nitrile having the formula R¹C═N; alternatively, an ether havingthe formula R²—O—R³; alternatively, a thioether having the formulaR⁴—S—R⁵; alternatively, an amine having the formula NR⁶R⁷R⁸, NHR⁶R⁷, orNH₂R⁶; alternatively, a phosphine having the formula PR⁹R¹⁰R¹¹, PHR⁹R¹⁰,or PH₂R⁹; or alternatively, a phosphine having the formula PR⁹R¹⁰R¹¹.

In an aspect, R¹ of the nitrile having the formula R¹C≡N, R² and R³ ofthe ether having formula R²—O—R³, R⁴ and R⁵ of the thioether having theformula R⁴—S—R⁵, R⁶, R⁷, and R⁸ of the amine having the formula NR⁶R⁷R⁸,NHR⁶R⁷, or NH₂R⁶ and R⁹, R^(m), and R¹¹ of the phosphine having theformula PR⁹R¹⁰R¹¹, PHR⁹R¹⁰, or PH₂R⁹, independently can be a C₁ to C₁₈hydrocarbyl group; alternatively, a C₁ to C₁₅ hydrocarbyl group;alternatively, a C₁ to C₁₂ hydrocarbyl group; alternatively, a C₁ to C₈hydrocarbyl group; or alternatively, a C₁ to C₆ hydrocarbyl group. Itshould also be noted that R² and R³ of the ether having formula R²—O—R³,R⁴ and R⁵ of the thioether having the formula R⁴—S—R⁵, any two of R⁶,R⁷, and R⁸ of the amine having the formula NR⁶R⁷R⁸ or NHR⁶R⁷, and/or anytwo of R⁹, R¹⁰, and R¹¹ of the phosphine having the formula PR⁹R¹⁰R¹¹ orPHR⁹R¹⁰ can be joined to form a ring containing the ether oxygen atom,the thioether sulfur atom, the amine nitrogen atom, or the phosphinephosphorus atom to form a cyclic ether, thioether, amine, or phosphine,respectively, as described herein in regards to cyclic ethers,thioethers, amines, and phosphines.

In an aspect, R¹ of the nitrile having the formula R¹C≡N, R² and R³ ofthe ether having formula R²—O—R³, R⁴ and R⁵ of the thioether having theformula R⁴—S—R⁵, R⁶, R⁷, and R⁸ of the amine having the formula NR⁶R⁷R⁸,NHR⁶R⁷, or NH₂R⁶ and R⁹, R¹⁰, and R¹¹ of the phosphine having theformula PR⁹R¹⁰R¹¹, PHR⁹R¹⁰ or PH₂R⁹, independently be any hydrocarbylgroup disclosed herein. The hydrocarbyl group can be, for instance, anyalkyl group, cycloalkyl group, aryl group, or aralkyl group disclosedherein.

In another aspect, each neutral ligand, L, in formula (II) independentlycan be a C₂-C₃₀ ether, a C₂-C₃₀ thioether, a C₂-C₂₀ nitrile, a C₁-C₃₀amine, or a C₁-C₃₀ phosphine; alternatively, a C₂-C₁₈ ether;alternatively, a C₂-C₁₈ thioether; alternatively, a C₂-C₁₂ nitrile;alternatively, a C₁-C₁₈ amine; or alternatively, a C₁-C₁₈ phosphine. Insome aspects, each neutral ligand independently can be a C₂-C₁₂ ether, aC₂-C₁₂ thioether, a C₂-C₈ nitrile, a C₁-C₁₂ amine, or a C₁-C₁₂phosphine; alternatively, a C₂-C₁₀ ether; alternatively, a C₂-C₁₀thioether; alternatively, a C₂-C₆ nitrile; alternatively, a C₁-C₈ amine;or alternatively, a C₁-C₈ phosphine.

Suitable ethers which can be utilized as a neutral ligand, either aloneor in combination, can include, but are not limited to, dimethyl ether,diethyl ether, dipropyl ether, dibutyl ether, methyl ethyl ether, methylpropyl ether, methyl butyl ether, diphenyl ether, ditolyl ether,tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,2,3-dihydrofuran, 2,5-dihydrofuran, furan, benzofuran, isobenzofuran,dibenzofuran, tetrahydropyran, 3,4-dihydro-2H-pyran,3,6-dihydro-2H-pyran, 2H-pyran, 4H-pyran, 1,3-dioxane, 1,4-dioxane,morpholine, and the like, including substituted derivatives thereof.

Suitable thioethers which can be utilized as a neutral ligand, eitheralone or in combination, can include, but are not limited to, dimethylthioether, diethyl thioether, dipropyl thioether, dibutyl thioether,methyl ethyl thioether, methyl propyl thioether, methyl butyl thioether,diphenyl thioether, ditolyl thioether, thiophene, benzothiophene,tetrahydrothiophene, thiane, and the like, including substitutedderivatives thereof.

Suitable nitriles which can be utilized as a neutral ligand, eitheralone or in combination, can include, but are not limited to,acetonitrile, propionitrile, butyronitrile, benzonitrile,4-methylbenzonitrile, and the like, including substituted derivativesthereof.

Suitable amines which can be utilized as a neutral ligand, either aloneor in combination, can include, but are not limited to, methyl amine,ethyl amine, propyl amine, butyl amine, dimethyl amine, diethyl amine,dipropyl amine, dibutyl amine, trimethyl amine, triethyl amine,tripropyl amine, tributyl amine, aniline, diphenylamine, triphenylamine,tolylamine, xylylamine, ditolylamine, pyridine, quinoline, pyrrole,indole, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine,2,5-dimethylpyrrole, 2,5-diethylpyrrole, 2,5-dipropylpyrrole,2,5-dibutylpyrrole, 2,4-dimethylpyrrole, 2,4-diethylpyrrole,2,4-dipropylpyrrole, 2,4-dibutylpyrrole, 3,4-dimethylpyrrole,3,4-diethylpyrrole, 3,4-dipropylpyrrole, 3,4-dibutylpyrrole,2-methylpyrrole, 2-ethylpyrrole, 2-propylpyrrole, 2-butylpyrrole,3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole,3-ethyl-2,4-dimethylpyrrole, 2,3,4,5-tetramethylpyrrole,2,3,4,5-tetraethylpyrrole, and the like, including substitutedderivatives thereof. Suitable amines can be primary amines, secondaryamines, or tertiary amines.

Suitable phosphines which can be utilized as a neutral ligand, eitheralone or in combination, can include, but are not limited to,trimethylphosphine, triethylphosphine, tripropylphosphine,tributylphosphine, phenylphosphine, tolylphosphine, diphenylphosphine,ditolylphosphine, triphenylphosphine, tritolylphosphine,methyldiphenylphosphine, dimethylphenylphosphine,ethyldiphenylphosphine, diethylphenylphosphine, and the like, includingsubstituted derivatives thereof.

In an aspect of the invention, each neutral ligand independently can beazetidine, oxetane, thietane, dioxetane, dithietane, tetrahydropyrrole,dihydropyrrole, pyrrole, indole, isoindole, tetrahydrofuran,2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, dihydrofuran,furan, benzofuran, isobenzofuran, tetrahydrothiophene, dihydrothiophene,thiophene, benzothiophene, isobenzothiophene, imidazolidine, pyrazole,imidazole, oxazolidine, oxazole, isoxazole, thiazolidine, thiazole,isothiazole, benzothiazole, dioxolane, dithiolane, triazole, dithiazole,piperidine, pyridine, dimethyl amine, diethyl amine, tetrahydropyran,dihydropyran, pyran, thiane, piperazine, diazine, oxazine, thiazine,dithiane, dioxane, dioxin, triazine, triazinane, trioxane, oxepin,azepine, thiepin, diazepine, morpholine, quinoline, tetrahydroquinone,bicyclo[3.3.1]tetrasiloxane, or acetonitrile; alternatively, azetidine,oxetane, thietane, dioxetane, dithietane, tetrahydropyrrole,tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,tetrahydrothiophene, imidazolidine, oxazolidine, oxazole, thiazolidine,thiazole, dioxolane, dithiolane, piperidine, tetrahydropyran, pyran,thiane, piperazine, oxazine, thiazine, dithiane, dioxane, dioxin,triazinane, trioxane, azepine, thiepin, diazepine, morpholine,1,2-thiazole, or bicyclo[3.3.1]tetrasiloxane; alternatively,tetrahydropyrrole, tetrahydrofuran, 2-methyltetrahydrofuran,2,5-dimethyltetrahydrofuran, tetrahydrothiophene, oxazolidine,thiazolidine, dioxolane, dithiolane, dithiazole, piperidine,tetrahydropyran, pyran, thiane, piperazine, dithiane, dioxane, dioxin,trioxane, or morpholine; alternatively, tetrahydrofuran,2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran,tetrahydrothiophene, dioxolane, dithiolane, tetrahydropyran, pyran,thiane, dithiane, dioxane, dioxin, or trioxane; alternatively,tetrahydrofuran, dioxolane, tetrahydropyran, dioxane, or trioxane;alternatively, pyrrole, furan, pyrazole, imidazole, oxazole, isoxazole,thiazole, isothiazole, triazole, pyridine, dimethyl amine, diethylamine, diazine, triazine, or quinoline; alternatively, pyrrole, furan,imidazole, oxazole, thiazole, triazole, pyridine, dimethyl amine,diethyl amine, diazine, or triazine; or alternatively, furan, oxazole,thiazole, triazole, pyridine, diazine, or triazine. In some aspects,each neutral ligand independently can be azetidine; alternatively,oxetane; alternatively, thietane; alternatively, dioxetane;alternatively, dithietane; alternatively, tetrahydropyrrole;alternatively, dihydropyrrole, alternatively, pyrrole; alternatively,indole; alternatively, isoindole; alternatively, tetrahydrofuran;alternatively, 2-methyltetrahydrofuran; alternatively,2,5-dimethyltetrahydrofuran; alternatively, dihydropyrrole;alternatively, furan; alternatively, benzofuran; alternatively,isobenzofuran; alternatively, tetrahydrothiophene; alternatively,dihydrothiophene; alternatively, thiophene; alternatively,benzothiophene; alternatively, isobenzothiophene; alternatively,imidazolidine; alternatively, pyrazole; alternatively, imidazole;alternatively, oxazolidine; alternatively, oxazole; alternatively,isoxazole; alternatively, thiazolidine; alternatively, thiazole;alternatively, benzothiazole; alternatively, isothiazole; alternatively,dioxolane; alternatively, dithiolane; alternatively, triazole;alternatively, dithiazole; alternatively, piperidine; alternatively,pyridine; alternatively, dimethyl amine; alternatively, diethyl amine;alternatively, tetrahydropyran; alternatively, dihydropyran;alternatively, pyran; alternatively, thiane; alternatively, piperazine;alternatively, diazine; alternatively, oxazine; alternatively, thiazine;alternatively, dithiane; alternatively, dioxane; alternatively, dioxin;alternatively, triazine; alternatively, triazinane; alternatively,trioxane; alternatively, oxepin; alternatively, azepine; alternatively,thiepin; alternatively, diazepine; alternatively, morpholine;alternatively, quinoline; alternatively, tetrahydroquinone;alternatively, bicyclo[3.3.1]tetrasiloxane; or alternatively,acetonitrile.

In another aspect, each neutral ligand independently can be azetidine,tetrahydropyrrole, dihydropyrrole, pyrrole, indole, isoindole,imidazolidine, pyrazole, imidazole, oxazolidine, oxazole, isoxazole,thiazolidine, thiazole, isothiazole, triazole, benzotriazole,dithiazole, piperidine, pyridine, dimethyl amine, diethyl amine,piperazine, diazine, oxazine, thiazine, triazine, azepine, diazepine,morpholine, quinoline, or tetrahydroisoquinoline. In another aspect,each neutral ligand independently can be thietane, dithietane,tetrahydrothiophene, dihydrothiophene, thiophene, benzothiophene,isobenzothiophene, thiazolidine, thiazole, isothiazole, dithiolane,dithiazole, thiane, thiazine, dithiane, or thiepin. In another aspect,each neutral ligand independently can be tetrahydrofuran, furan,methyltetrahydrofuran, dihydrofuran, tetrahydropyran, 2,3-dihydropyran,1,3-dioxane, 1,4-dioxane, morpholine, N-methylmorpholine, acetonitrile,propionitrile, butyronitrile, benzonitrile, pyridine, ammonia, methylamine, ethyl amine, dimethyl amine, diethyl amine, trimethyl amine,triethyl amine, trimethylphosphine, triethylphosphine,triphenylphosphine, tri-n-butylphosphine, methyl isocyanide, n-butylisocyanide, phenyl isocyanide, SMe₂, thiophene, or tetrahydrothiophene.In another aspect, each neutral ligand independently can betetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, 1,4-dioxane,acetonitrile, pyridine, dimethyl amine, diethyl amine, ammonia,trimethyl amine, triethyl amine, trimethylphosphine, triethylphosphine,triphenylphosphine, SMe₂, or tetrahydrothiophene; alternatively,tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, or 1,4-dioxane;alternatively, ammonia, trimethylamine, or triethylamine; oralternatively, trimethylphosphine, triethylphosphine, ortriphenylphosphine. Yet, in another aspect, each neutral ligandindependently can be tetrahydrofuran, acetonitrile, pyridine, ammonia,dimethyl amine, diethyl amine, trimethyl amine, trimethylphosphine, ortriphenylphosphine; alternatively, tetrahydrofuran, acetonitrile,pyridine, dimethyl amine, diethyl amine, trimethyl amine,trimethylphosphine, or triphenylphosphine; alternatively,tetrahydrofuran, acetonitrile, dimethyl amine, diethyl amine, orpyridine; alternatively, tetrahydrofuran; alternatively, acetonitrile;alternatively, dimethyl amine; alternatively, diethyl amine; oralternatively, pyridine.

Methods of the present invention can be practiced with a variety ofcatalyst compositions. In one aspect, the catalyst composition cancomprise a transition metal compound or complex (e.g., any transitionmetal complex or compound disclosed herein, such as a metallocenecompound, a compound having formula (II), etc.) and an activator, whilein another aspect, the catalyst composition can comprise a transitionmetal complex, an activator, and a co-catalyst. These catalystcompositions can be utilized to produce polyolefins—homopolymers,copolymers, and the like—for a variety of end-use applications.

Transition metal complexes or compounds, including those with formula(II), were discussed above. In aspects of the present invention, it iscontemplated that the catalyst composition can contain more than onetransition metal compound, such as, for instance, a dual catalystsystem. Additionally, more than one activator (e.g., aluminoxane,chemically-treated solid oxide, etc.) also may be utilized.

Generally, catalyst compositions of the present invention can comprise atransition metal complex and an activator, and in some aspects, theactivator can comprise an activator-support. Activator-supports usefulin the present invention were disclosed above. Such catalystcompositions can further comprise one or more than one co-catalyst orco-catalysts (suitable co-catalysts, such as organoaluminum compounds,also were discussed above). Thus, a catalyst composition of thisinvention can comprise a transition metal complex (e.g., a metallocenecompound, a compound having formula (II), etc.), an activator-support,and an organoaluminum compound. For instance, the activator-support cancomprise (or consist essentially of, or consist of) fluorided alumina,chlorided alumina, bromided alumina, sulfated alumina, fluoridedsilica-alumina, chlorided silica-alumina, bromided silica-alumina,sulfated silica-alumina, fluorided silica-zirconia, chloridedsilica-zirconia, bromided silica-zirconia, sulfated silica-zirconia,fluorided silica-titania, fluorided silica-coated alumina, sulfatedsilica-coated alumina, phosphated silica-coated alumina, and the like,or combinations thereof. Additionally, the organoaluminum compound cancomprise (or consist essentially of, or consist of) trimethylaluminum,triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Accordingly, a catalystcomposition consistent with aspects of the invention can comprise (orconsist essentially of, or consist of) a transition metal compound,sulfated alumina (or fluorided silica-alumina), and triethylaluminum (ortriisobutylaluminum).

In another aspect of the present invention, a catalyst composition isprovided which comprises a transition metal complex, anactivator-support, and an organoaluminum compound, wherein this catalystcomposition is substantially free of aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, and/or other similarmaterials; alternatively, substantially free of aluminoxanes;alternatively, substantially free or organoboron or organoboratecompounds; or alternatively, substantially free of ionizing ioniccompounds. In these aspects, the catalyst composition has catalystactivity in the absence of these additional materials. For example, acatalyst composition of the present invention can consist essentially ofa transition metal complex, an activator-support, and an organoaluminumcompound, wherein no other materials are present in the catalystcomposition which would increase/decrease the activity of the catalystcomposition by more than about 10% from the catalyst activity of thecatalyst composition in the absence of said materials.

However, in other aspects of this invention, theseactivators/co-catalysts can be employed. For example, a catalystcomposition comprising a transition metal complex and anactivator-support can further comprise an optional co-catalyst. Suitableco-catalysts in this aspect include, but are not limited to, analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, an organoaluminum compound, an organomagnesiumcompound, an organolithium compound, and the like, or any combinationthereof. More than one co-catalyst can be present in the catalystcomposition.

In a different aspect, a catalyst composition is provided which does notrequire an activator-support. Such a catalyst composition can comprise atransition metal complex and an activator, wherein the activatorcomprises an aluminoxane compound, an organoboron or organoboratecompound, an ionizing ionic compound, or combinations thereof.Optionally, such catalyst compositions can further comprise aco-catalyst (e.g., an organoaluminum compound).

This invention further encompasses any methods of making these catalystcompositions, such as, for example, contacting the respective catalystcomponents in any order or sequence.

The transition metal complex (e.g., a metallocene compound, a compoundhaving formula (II), etc.) can be precontacted with an olefinic monomerif desired, not necessarily the olefin monomer to be polymerized, and anorganoaluminum compound for a first period of time prior to contactingthis precontacted mixture with an activator-support. The first period oftime for contact, the precontact time, between the transition metalcomplex, the olefinic monomer, and the organoaluminum compound typicallyranges from a time period of about 1 minute to about 24 hours, forexample, from about 3 minutes to about 1 hour. Precontact times fromabout 10 minutes to about 30 minutes are also employed. Alternatively,the precontacting process is carried out in multiple steps, rather thana single step, in which multiple mixtures are prepared, each comprisinga different set of catalyst components. For example, at least twocatalyst components are contacted forming a first mixture, followed bycontacting the first mixture with at least one other catalyst componentforming a second mixture, and so forth.

Multiple precontacting steps can be carried out in a single vessel or inmultiple vessels. Further, multiple precontacting steps can be carriedout in series (sequentially), in parallel, or a combination thereof. Forexample, a first mixture of two catalyst components can be formed in afirst vessel, a second mixture comprising the first mixture plus oneadditional catalyst component can be formed in the first vessel or in asecond vessel, which is typically placed downstream of the first vessel.

In another aspect, one or more of the catalyst components can be splitand used in different precontacting treatments. For example, part of acatalyst component is fed into a first precontacting vessel forprecontacting with at least one other catalyst component, while theremainder of that same catalyst component is fed into a secondprecontacting vessel for precontacting with at least one other catalystcomponent, or is fed directly into the reactor, or a combinationthereof. The precontacting can be carried out in any suitable equipment,such as tanks, stirred mix tanks, various static mixing devices, aflask, a vessel of any type, or combinations of these apparatus.

In another aspect of this invention, the various catalyst components(for example, a transition metal complex, activator-support,organoaluminum co-catalyst, and optionally an unsaturated hydrocarbon)can be contacted in the polymerization reactor simultaneously while thepolymerization reaction is proceeding. Alternatively, any two or more ofthese catalyst components can be precontacted in a vessel prior toentering the reaction zone. This precontacting step can be continuous,in which the precontacted product is fed continuously to the reactor, orit can be a stepwise or batchwise process in which a batch ofprecontacted product is added to make a catalyst composition. Thisprecontacting step can be carried out over a time period that can rangefrom a few seconds to as much as several days, or longer. In thisaspect, the continuous precontacting step generally lasts from about 1second to about 1 hour. In another aspect, the continuous precontactingstep lasts from about 10 seconds to about 45 minutes, or from about 1minute to about 30 minutes.

Once the precontacted mixture of the transition metal compound, theolefin monomer, and the organoaluminum co-catalyst is contacted with theactivator-support, this composition (with the addition of theactivator-support) is termed the “postcontacted mixture.” Thepostcontacted mixture optionally can remain in contact for a secondperiod of time, the postcontact time, prior to initiating thepolymerization process. Postcontact times between the precontactedmixture and the activator-support generally range from about 1 minute toabout 24 hours. In a further aspect, the postcontact time is in a rangefrom about 3 minutes to about 1 hour. The precontacting step, thepostcontacting step, or both, can increase the productivity of thepolymer as compared to the same catalyst composition that is preparedwithout precontacting or postcontacting. However, neither aprecontacting step nor a postcontacting step is required.

The postcontacted mixture can be heated at a temperature and for a timeperiod sufficient to allow adsorption, impregnation, or interaction ofprecontacted mixture and the activator-support, such that a portion ofthe components of the precontacted mixture is immobilized, adsorbed, ordeposited thereon. Where heating is employed, the postcontacted mixturegenerally can be heated to a temperature of from between about −15° C.to about 70° C., or from about 0° C. to about 40° C.

When a precontacting step is used, the molar ratio of the total moles ofolefin monomer to total moles of transition metal compound(s) in theprecontacted mixture typically can be in a range from about 1:10 toabout 100,000:1. Total moles of each component are used in this ratio toaccount for aspects of this invention where more than one olefin monomerand/or more than one transition metal complex is employed in aprecontacting step. Further, this molar ratio can be in a range fromabout 10:1 to about 1,000:1 in another aspect of the invention.

Generally, the weight ratio of organoaluminum compound toactivator-support can be in a range from about 10:1 to about 1:1000. Ifmore than one organoaluminum compound and/or more than oneactivator-support is employed, this ratio is based on the total weightof each respective component. In another aspect, the weight ratio of theorganoaluminum compound to the activator-support can be in a range fromabout 3:1 to about 1:100, or from about 1:1 to about 1:50.

In some aspects of this invention, the weight ratio of transition metalcompound(s) to activator-support can be in a range from about 1:1 toabout 1:1,000,000. If more than one activator-support is employed, thisratio is based on the total weight of the activator-support. In anotheraspect, this weight ratio can be in a range from about 1:5 to about1:100,000, or from about 1:10 to about 1:10,000. Yet, in another aspect,the weight ratio of the transition metal compound(s) to theactivator-support can be in a range from about 1:20 to about 1:1000.

Interestingly, in some aspects of the present invention, the catalystactivity of the catalyst composition using the synergistic amount ofhydrogen and the organozinc compound to produce an olefin polymer with apredetermined Mw (or MI) can be greater than a catalyst activity of thecatalyst composition obtained under the same polymerization conditionsusing hydrogen only (i.e., without the organozinc compound) to producean olefin polymer with the same predetermined Mw (or MI). Catalystactivity increases can be in a range of from about 5% to about 50%, orfrom about 10% to about 40%, for example. While not wishing to be boundby theory, Applicants believe that this improvement in catalyst activitymay be particularly noticeable for olefin polymers having apredetermined MI that falls within a range from about 1 to about 6 g/10min. For instance, for an olefin polymer having a MI of about 4 g/10min, the catalyst activity of the catalyst composition using thesynergistic amount of hydrogen and the organozinc compound to producethe olefin polymer with a MI of 4 can be at least about 10% greater, atleast about 20% greater, at least about 25% greater, or at least about30% greater, than the catalyst activity of the catalyst compositionobtained under the same polymerization conditions using hydrogen only(without the organozinc compound) to produce the olefin polymer with aMI of 4. While not limited to specific polymerization conditions(temperature, pressure, polymerization process, etc.), particularconditions that may be useful in some aspects of the invention tomeasure or determine catalyst activity can include: slurrypolymerization conditions, using isobutane as the diluent, at apolymerization temperature of about 80° C. (or about 90° C., or about100° C.) and a reactor pressure of about 490 psig (3.4 MPa), or about550 psig (3.8 MPa), or about 580 psig (4 MPa).

As discussed above, any combination of the transition metal compound,the activator-support, the organoaluminum compound, and the olefinmonomer, can be precontacted in some aspects of this invention. When anyprecontacting occurs with an olefinic monomer, it is not necessary thatthe olefin monomer used in the precontacting step be the same as theolefin to be polymerized. Further, when a precontacting step among anycombination of the catalyst components is employed for a first period oftime, this precontacted mixture can be used in a subsequentpostcontacting step between any other combination of catalyst componentsfor a second period of time. For example, the transition metal compound,the organoaluminum compound, and 1-hexene can be used in a precontactingstep for a first period of time, and this precontacted mixture then canbe contacted with the activator-support to form a postcontacted mixturethat is contacted for a second period of time prior to initiating thepolymerization reaction. For example, the first period of time forcontact, the precontact time, between any combination of the transitionmetal compound, the olefinic monomer, the activator-support, and theorganoaluminum compound can be from about 1 minute to about 24 hours,from about 3 minutes to about 1 hour, or from about 10 minutes to about30 minutes. The postcontacted mixture optionally is allowed to remain incontact for a second period of time, the postcontact time, prior toinitiating the polymerization process. According to one aspect of thisinvention, postcontact times between the precontacted mixture and anyremaining catalyst components is from about 1 minute to about 24 hours,or from about 5 minutes to about 1 hour.

Olefin Monomers

Olefin monomers contemplated herein typically include olefin compoundshaving from 2 to 30 carbon atoms per molecule and having at least oneolefinic double bond. Homopolymerization processes using a singleolefin, such as ethylene, propylene, butene, hexene, octene, and thelike, are encompassed, as well as copolymerization, terpolymerization,etc., reactions using an olefin monomer with at least one differentolefinic compound.

As an example, any resultant ethylene copolymers, terpolymers, etc.,generally can contain a major amount of ethylene (>50 mole percent) anda minor amount of comonomer (<50 mole percent). Comonomers that can becopolymerized with ethylene often have from 3 to 20 carbon atoms intheir molecular chain.

Acyclic, cyclic, polycyclic, terminal (a), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed. For example, typical unsaturated compounds thatcan be polymerized to produce olefin polymers can include, but are notlimited to, ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene,isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 2-hexene, 3-hexene, 3-ethyl-1-hexene,1-heptene, 2-heptene, 3-heptene, the four normal octenes (e.g.,1-octene), the four normal nonenes, the five normal decenes, and thelike, or mixtures of two or more of these compounds. Cyclic and bicyclicolefins, including but not limited to, cyclopentene, cyclohexene,norbornylene, norbornadiene, and the like, also can be polymerized asdescribed herein. Styrene also can be employed as a monomer or as acomonomer. In some aspects, the olefin monomer can comprise a C₂-C₂₀olefin; alternatively, a C₂-C₁₂ olefin; alternatively, a C₂-C₁₀α-olefin; alternatively, ethylene, propylene, 1-butene, 1-hexene, or1-octene; alternatively, ethylene or propylene; alternatively, ethylene;or alternatively, propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer can be, for example, ethylene or propylene, which iscopolymerized with at least one comonomer. According to one aspect, theolefin monomer in the polymerization process can comprise ethylene. Inthis aspect, examples of suitable olefin comonomers can include, but arenot limited to, propylene, 1-butene, 2-butene, 3-methyl-1-butene,isobutylene, 1-pentene, 2-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 1-hexene, 2-hexene, 3-ethyl-1-hexene, 1-heptene,2-heptene, 3-heptene, 1-octene, 1-decene, styrene, and the like, orcombinations thereof. According to one aspect, the comonomer cancomprise a C₃-C₁₆ α-olefin, while in another aspect, the comonomer cancomprise 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, styrene, orany combination thereof. For example, ethylene can be the olefinmonomer, and the olefin comonomer can comprise 1-butene, 1-hexene,1-octene, or a combination thereof.

Generally, the amount of comonomer introduced into a polymerizationreactor to produce the copolymer can be from about 0.01 to about 50weight percent of the comonomer based on the total weight of the monomerand comonomer. According to another aspect, the amount of comonomerintroduced into a polymerization reactor can be from about 0.01 to about40 weight percent comonomer based on the total weight of the monomer andcomonomer. In still another aspect, the amount of comonomer introducedinto a polymerization reactor can be from about 0.1 to about 35 weightpercent comonomer based on the total weight of the monomer andcomonomer. Yet, in another aspect, the amount of comonomer introducedinto a polymerization reactor can be from about 0.5 to about 20 weightpercent comonomer based on the total weight of the monomer andcomonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization reaction. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight.

According to one aspect, at least one monomer/reactant can be ethylene,so the polymerization reaction can be a homopolymerization involvingonly ethylene, or a copolymerization with a different acyclic, cyclic,terminal, internal, linear, branched, substituted, or unsubstitutedolefin. In addition, the methods disclosed herein intend for olefin toalso encompass diolefin compounds that include, but are not limited to,1,3-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, and the like.

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer (and optional comonomer(s)) described herein. Forexample, the olefin polymer can comprise an ethylene homopolymer, apropylene homopolymer, an ethylene copolymer (e.g., ethylene/1-butene,ethylene/1-hexene, ethylene/1-octene, etc.), a propylene copolymer, anethylene terpolymer, a propylene terpolymer, and the like, includingcombinations thereof.

Polymerization Reactor Systems

The disclosed methods are intended for any olefin polymerization processusing various types of polymerization reactors, polymerization reactorsystems, and polymerization reaction conditions. As used herein,“polymerization reactor” includes any polymerization reactor capable ofpolymerizing (inclusive of oligomerizing) olefin monomers and comonomers(one or more than one comonomer) to produce homopolymers, copolymers,terpolymers, and the like. The various types of polymerization reactorsinclude those that can be referred to as a batch reactor, slurryreactor, gas-phase reactor, solution reactor, high pressure reactor,tubular reactor, autoclave reactor, and the like, or combinationsthereof. The polymerization conditions for the various reactor types arewell known to those of skill in the art. Gas phase reactors can comprisefluidized bed reactors or staged horizontal reactors. Slurry reactorscan comprise vertical or horizontal loops. High pressure reactors cancomprise autoclave or tubular reactors. Reactor types can include batchor continuous processes. Continuous processes could use intermittent orcontinuous product discharge. Polymerization reactor systems andprocesses also can include partial or full direct recycle of unreactedmonomer, unreacted comonomer, and/or diluent.

A polymerization reactor system can comprise one type of reactor ormultiple reactors of the same or different type. For instance, thepolymerization reactor system can comprise a slurry reactor, a gas-phasereactor, a solution reactor, or a combination of two or more of thesereactors. Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactor(s).Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both.

According to one aspect, the polymerization reactor system can compriseat least one loop slurry reactor comprising vertical or horizontalloops. Monomer, diluent, catalyst, and comonomer can be continuously fedto a loop reactor where polymerization occurs. Generally, continuousprocesses can comprise the continuous introduction of monomer/comonomer,a catalyst, and a diluent into a polymerization reactor and thecontinuous removal from this reactor of a suspension comprising polymerparticles and the diluent. Reactor effluent can be flashed to remove thesolid polymer from the liquids that comprise the diluent, monomer and/orcomonomer. Various technologies can be used for this separation stepincluding, but not limited to, flashing that can include any combinationof heat addition and pressure reduction; separation by cyclonic actionin either a cyclone or hydrocyclone; or separation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, and 6,833,415,each of which is incorporated herein by reference in its entirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under reaction conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used. An example is polymerization ofpropylene monomer as disclosed in U.S. Pat. No. 5,455,314, which isincorporated by reference herein in its entirety.

According to yet another aspect, the polymerization reactor system cancomprise at least one gas phase reactor (e.g., a fluidized bed reactor).Such reactor systems can employ a continuous recycle stream containingone or more monomers continuously cycled through a fluidized bed in thepresence of the catalyst under polymerization conditions. A recyclestream can be withdrawn from the fluidized bed and recycled back intothe reactor. Simultaneously, polymer product can be withdrawn from thereactor and new or fresh monomer can be added to replace the polymerizedmonomer. Such gas phase reactors can comprise a process for multi-stepgas-phase polymerization of olefins, in which olefins are polymerized inthe gaseous phase in at least two independent gas-phase polymerizationzones while feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790, and5,436,304, each of which is incorporated by reference in its entiretyherein.

According to still another aspect, the polymerization reactor system cancomprise a high pressure polymerization reactor, e.g., can comprise atubular reactor or an autoclave reactor. Tubular reactors can haveseveral zones where fresh monomer, initiators, or catalysts are added.Monomer can be entrained in an inert gaseous stream and introduced atone zone of the reactor. Initiators, catalysts, and/or catalystcomponents can be entrained in a gaseous stream and introduced atanother zone of the reactor. The gas streams can be intermixed forpolymerization. Heat and pressure can be employed appropriately toobtain optimal polymerization reaction conditions.

According to yet another aspect, the polymerization reactor system cancomprise a solution polymerization reactor wherein the monomer/comonomerare contacted with the catalyst composition by suitable stirring orother means. A carrier comprising an inert organic diluent or excessmonomer can be employed. If desired, the monomer/comonomer can bebrought in the vapor phase into contact with the catalytic reactionproduct, in the presence or absence of liquid material. Thepolymerization zone can be maintained at temperatures and pressures thatwill result in the formation of a solution of the polymer in a reactionmedium. Agitation can be employed to obtain better temperature controland to maintain uniform polymerization mixtures throughout thepolymerization zone. Adequate means are utilized for dissipating theexothermic heat of polymerization.

The polymerization reactor system can further comprise any combinationof at least one raw material feed system, at least one feed system forcatalyst or catalyst components, and/or at least one polymer recoverysystem. Suitable reactor systems can further comprise systems forfeedstock purification, catalyst storage and preparation, extrusion,reactor cooling, polymer recovery, fractionation, recycle, storage,loadout, laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 60°C. to about 280° C., for example, or from about 60° C. to about 110° C.,depending upon the type of polymerization reactor. In some reactorsystems, the polymerization temperature generally can be within a rangefrom about 70° C. to about 90° C., or from about 75° C. to about 85° C.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). The pressurefor gas phase polymerization is usually in the 200 to 500 psig range(1.4 MPa to 3.4 MPa). High pressure polymerization in tubular orautoclave reactors generally can be conducted at about 20,000 to 75,000psig (138 to 517 MPa). Polymerization reactors can also be operated in asupercritical region occurring at generally higher temperatures andpressures. Operation above the critical point of a pressure/temperaturediagram (supercritical phase) may offer advantages.

As an example, a representative set of polymerization conditions caninclude, among others, a polymerization reaction temperature in a rangefrom about 60° C. to about 110° C. (or from about 70° C. to about 90°C.), and a reaction pressure in a range from about 200 to about 1000psig (about 1.4 to about 6.9 MPa).

The concentration of the reactants entering the polymerization reactorcan be controlled to produce resins with certain physical and mechanicalproperties. The proposed end-use product that will be formed by thepolymer resin and the method of forming that product ultimately candetermine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymersproduced by any of the polymerization processes and methods disclosedherein. Articles of manufacture can be formed from, and/or can comprise,the polymers produced in accordance with this invention.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, maysuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

The sulfated alumina activator-support used in the examples was preparedas follows. Bohemite was obtained from W.R. Grace Company under thedesignation “Alumina A” and having a surface area of about 300 m²/g anda pore volume of about 1.3 mL/g This material was obtained as a powderhaving an average particle size of about 100 microns. This material wasimpregnated to incipient wetness with an aqueous solution of ammoniumsulfate to equal about 15% sulfate. This mixture was then placed in aflat pan and allowed to dry under vacuum at approximately 110° C. forabout 16 hours. To calcine the resultant powdered mixture, the materialwas fluidized in a stream of dry air at about 550° C. for about 6 hours.Afterward, the sulfated alumina was collected and stored under drynitrogen, and was used without exposure to the atmosphere.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight.

High load melt index (HLMI, g/10 min) was determined in accordance withASTM D1238 at 190° C. with a 21,600 gram weight.

Molecular weights and molecular weight distributions were obtained usinga PL 220 high temperature GPC/SEC unit (Polymer Laboratories, now anAgilent company) with 1,2,4-trichlorobenzene (TCB) as the solvent, andwith a flow rate of 1 mL/min at a temperature of 145° C.2,6-di-tert-butyl-4-methylphenol (BHT) at a concentration of 0.5 g/L wasadded to the solvent as a stabilizer. An injection volume of 400 μL wasused with a nominal polymer concentration of 1.5 mg/mL. Dissolution ofthe sample in stabilized TCB was carried out by heating at 150° C. for 5hr or longer, depending upon the sample, with occasional gentleagitation. The columns used were three Waters Styragel HMW-6E columns(7.8×300 mm) (Waters Corp., MA), and were calibrated with the broadcalibration method using a broad linear polyethylene standard (ChevronPhillips Chemical Company Marlex® BHB 5003), whose molecular weight andmolecular weight distribution had been determined separately.

Mn is the number-average molecular weight (g/mol); Mw is theweight-average molecular weight (g/mol); Mz is the z-average molecularweight (g/mol); My is the viscosity-average molecular weight (g/mol);and Mp is the peak molecular weight.

Examples 1-5 Polymerization Experiments Using Hydrogen and/orDiethylzinc (DEZ)

All polymerization experiments were conducted for either 30 min or 60min in a one-gallon (3.8-L) stainless-steel autoclave reactor containingtwo liters of isobutane as diluent. Sulfated alumina was used as theactivator. The metallocene compound was pentamethylcyclopentadienylchromium dichloride, and the neutral ligand was pyridine, with zero orone coordinated with the metallocene compound. A solution of themetallocene was prepared by dissolving about 2 mg of the metallocenecompound in about 2 mL of toluene.

Example 1

Under isobutane purge, 0.5 mL of a TIBA solution (25% in heptanes) werecharged to a cold reactor, followed by 1 mL of the metallocene solution,and 0.2 g of the sulfated alumina The reactor was sealed, 2 L ofisobutane were added, and stirring was initiated at 700 rpm. As thereactor temperature approached the target run temperature of 105° C.,ethylene and hydrogen (molar ratio of H₂/C₂=0.1) were added to maintaina reactor pressure of 584 psi (4 MPa) throughout the run. The reactorwas maintained at 105° C. for 60 min, and then the volatiles were ventedfrom the reactor. Solid polyethylene was collected from the reactor (297g).

Example 2

Under isobutane purge, 0.5 mL of a TIBA solution (25% in heptanes) and0.2 mL of DEZ (14.3% in heptanes) were charged to a cold reactor,followed by 1 mL of the metallocene solution, and 0.2 g of the sulfatedalumina. The reactor was sealed, 2 L of isobutane were added, andstirring was initiated at 700 rpm. As the reactor temperature approachedthe target run temperature of 105° C., ethylene and hydrogen (molarratio of H₂/C₂=0.1) were added to maintain a reactor pressure of 584 psi(4 MPa). The reactor was maintained at 105° C. for 60 min, and then thevolatiles were vented from the reactor. Solid polyethylene was collectedfrom the reactor (288 g).

Example 3

Under isobutane purge, 0.5 mL of a TIBA solution (25% in heptanes) werecharged to a cold reactor, followed by 1 mL of the metallocene solution,and 0.2 g of the sulfated alumina The reactor was sealed, 2 L ofisobutane were added, and stirring was initiated at 700 rpm. As thereactor temperature approached the target run temperature of 105° C.,ethylene was added to maintain a reactor pressure of 490 psi (3.4 MPa)throughout the run. The reactor was maintained at 105° C. for 30 min,and then the volatiles were vented from the reactor. Solid polyethylenewas collected from the reactor (182 g).

Example 4

Under isobutane purge, 0.5 mL of a TIBA solution (25% in heptanes) and0.2 mL of DEZ (14.3% in heptanes) were charged to a cold reactor,followed by 1 mL of the metallocene solution, and 0.2 g of the sulfatedalumina. The reactor was sealed, 2 L of isobutane were added, andstirring was initiated at 700 rpm. As the reactor temperature approachedthe target run temperature of 105° C., ethylene was added to maintain areactor pressure of 490 psi (3.4 MPa). The reactor was maintained at105° C. for 30 min, and then the volatiles were vented from the reactor.Solid polyethylene was collected from the reactor (171 g).

Example 5

Under isobutane purge, 0.5 mL of a TIBA solution (25% in heptanes) and 5mL of DEZ (14.3% in heptanes) were charged to a cold reactor, followedby 1 mL of the metallocene solution, and 0.2 g of the sulfated alumina.The reactor was sealed, 2 L of isobutane were added, and stirring wasinitiated at 700 rpm. As the reactor temperature approached the targetrun temperature of 105° C., ethylene was added to maintain a reactorpressure of 490 psi (3.4 MPa). The reactor was maintained at 105° C. for30 min, and then the volatiles were vented from the reactor. Solidpolyethylene was collected from the reactor (143 g).

Table I summarizes certain polymerization reaction conditions, catalystactivities (grams of polyethylene), and polymer properties for Examples1-5. The DEZ concentration was based on the total liquid volume in thereactor. FIG. 1 illustrates the molecular weight distributions of thepolymers of Examples 1-2, and FIG. 2 illustrates the molecular weightdistributions of the polymers of Examples 3-5.

As compared to Example 3, the addition of DEZ in Examples 4-5 hadrelatively little effect on MI, HLMI, Mw, Mz, and Mv. As compared toExample 3, the addition of hydrogen in Example 1 increased the MI andHLMI and decreased all molecular weight parameters, but at the sametime, the catalyst activity was reduced. Unexpectedly, the addition ofhydrogen and DEZ in Example 2 resulted in a synergistic reduction in Mw,Mz, Mv, and Mp, and a synergistic increase in MI and HLMI. Forcomparison, see the individual effect of hydrogen in Example 1 and theindividual effect of DEZ in Example 4. Moreover, Mn was largelyunaffected in Example 2.

Constructive Examples 6-7 Constructive Polymerization Experiments withand without Hydrogen and an Organozinc Compound

A production-scale loop slurry reactor running under standardpolymerization conditions is used. The reactor size is about 27,000 gal(102 kL), the reactor temperature is in the 80-120° C. range (e.g., 105°C.), the reactor pressure is in the 2.7-5.1 MPa psig range (e.g.,3.4-4.1 MPa), and the ethylene weight percent is in the 3-9.5% range(e.g., 5-7%). A comonomer, such as 1-hexene, can be added to thepolymerization reactor to produce an olefin polymer having a densitywithin the 0.89-0.95 g/cm³ range, for instance, a density in the0.91-0.93 g/cm³ range. However, in Constructive Examples 6-7, nocomonomer is added. The catalyst composition for these ConstructiveExamples can include a metallocene compound (e.g.,pentamethylcyclopentadienyl chromium dichloride), an activator-support(e.g., sulfated alumina), and an organoaluminum (e.g., TIBA).

Constructive Example 6 does not utilize hydrogen and an organozinccompound (e.g., DEZ), while Constructive Example 7 utilizes asynergistic amount of hydrogen and an organozinc compound (e.g., DEZ).The olefin polymer produced in Constructive Example 6 can be an ethylenehomopolymer having a Mw of about 1,000,000 g/mol, and a MI and HLMI thatcannot be measured (i.e., too low). This polymer can be produced at aproduction rate in a range of about 11,500 to about 16,000 kg/hr. InConstructive Example 7, hydrogen can be added to the reactor at ahydrogen:ethylene monomer molar ratio in the 0.01:1 to 0.2:1 range(e.g., a molar ratio of 0.1:1). DEZ can be added directly to the reactorat a feed rate that provides a hydrogen:DEZ molar ratio in the 100:1 to25,000:1 range (e.g., a molar ratio of 500:1, or 2, 500:1, or 5,000:1).At generally the same production rate as Constructive Example 6, theolefin polymer of Constructive Example 7 can be produced: an ethylenehomopolymer having a MI of greater than 1 (e.g., a nominal MI of 4) anda Mw of less than 200,000 g/mol (e.g., a Mw of 100,000 g/mol). Thus, theaddition of the synergistic amount of hydrogen and the organozinccompound (e.g., DEZ) in Constructive Example 7 can reduce Mw andincrease MI as compared to Constructive Example 6. The synergisticamount of hydrogen and the organozinc compound (e.g., DEZ) can be variedthroughout the production run of the olefin polymer of ConstructiveExample 7 in order to control the desired polymer properties, such as MIand Mw, amongst other properties. It is expected that any variation inthe respective amounts of hydrogen and the organozinc compound duringthe course of the production run (i.e., to produce the nominal 4 MIpolyethylene) can be within the hydrogen:organozinc compound molar ratiorange of 100:1 to 25,000:1 (or in the 200:1 to 20,000:1 range, or in the500:1 to 5000:1 range).

TABLE I Summary of Examples 1-5 H₂/Ethylene [DEZ] H₂/DEZ MI HLMI RunTime PE Example (molar ratio) (mmol/L) (molar ratio) (g/10 min) (g/10min) HLMI/MI (min) (grams) 1 0.1 0 N/A 1.28 49 38 60 297 2 0.1 0.08452,300 4.58 150 33 60 288 3 0 0 N/A too low too low N/A 30 182 4 0 0.08450 too low too low N/A 30 171 5 0 2.1125 0 too low too low N/A 30 143Mn/1000 Mw/1000 Mz/1000 Mv/1000 Mp/1000 Example (g/mol) (g/mol) (g/mol)(g/mol) (g/mol) Mw/Mn Mz/Mw 1 9.4 180 1898 127 73 19.2 10.52 2 10.0 96337 78 59 9.6 3.50 3 11.3 1014 2877 809 830 89.4 2.84 4 9.8 1063 3024839 1210 108.2 2.85 5 44.7 932 2528 774 650 20.9 2.71

1. A method of controlling a polymerization reaction in a polymerizationreactor system, the method comprising: (i) introducing a transitionmetal-based catalyst composition, an olefin monomer, and optionally anolefin comonomer into a polymerization reactor within the polymerizationreactor system, wherein the transition metal-based catalyst compositioncomprises (a) a transition metal compound; (b) an activator-supportcomprising a solid oxide treated with an electron-withdrawing anion; and(c) optionally, a co-catalyst; (ii) contacting the transitionmetal-based catalyst composition with the olefin monomer and theoptional olefin comonomer under polymerization conditions to produce anolefin polymer; and (iii) introducing a synergistic amount of hydrogenand an organozinc compound into the polymerization reactor system toreduce a weight-average molecular weight (Mw) and/or to increase a meltindex (MI) of the olefin polymer.
 2. The method of claim 1, wherein theorganozinc compound comprises a compound having the formula:Zn(X¹⁰)(X¹¹); wherein: X¹⁰ is a C₁ to C₁₈ hydrocarbyl group; and X¹¹ isH, a halide, or a C₁ to C₁₈ hydrocarbyl or C₁ to C₁₈ hydrocarboxy group.3. The method of claim 1, wherein the organozinc compound comprisesdiethylzinc.
 4. The method of claim 1, wherein the transitionmetal-based catalyst composition comprises chromium, vanadium, titanium,zirconium, hafnium, or a combination thereof. 5-7. (canceled)
 8. Themethod of claim 1, wherein: the activator-support comprises fluoridedalumina, chlorided alumina, bromided alumina, sulfated alumina,fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or any combination thereof; and the co-catalyst comprises anorganoaluminum compound, the organoaluminum compound comprisingtrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, or any combination thereof.
 9. Themethod of claim 1, wherein the transition metal compound has theformula:Cr(X^(A))(X¹)(X²)(L)_(n); wherein: X^(A) is a substituted orunsubstituted cyclopentadienyl, indenyl, or fluorenyl group; X¹ and X²independently are a monoanionic ligand; and L is a neutral ligand,wherein n is 0, 1, or
 2. 10. The method of claim 9, wherein: X^(A) is asubstituted cyclopentadienyl group; X¹ and X² independently arehydrogen, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆hydrocarbyloxy group, a C₁ to C₃₆ hydrocarbylaminyl group, a C₁ to C₃₆hydrocarbylsilyl group, a C₁ to C₃₆ hydrocarbylaminylsilyl group,OBR^(A) ₂, or OSO₂R^(A), wherein R^(A) is a C₁ to C₃₆ hydrocarbyl group;and L is an ether, a thioether, an amine, a nitrile, or a phosphine. 11.The method of claim 1, wherein the olefin monomer comprises a C₂-C₂₀olefin.
 12. The method of claim 1, wherein the olefin monomer comprisesethylene.
 13. The method of claim 1, wherein the polymerization reactorsystem comprises a slurry reactor, a gas-phase reactor, a solutionreactor, or a combination thereof.
 14. The method of claim 1, whereinhydrogen is added to the polymerization reactor system at ahydrogen:olefin monomer molar ratio in a range from about 0.01:1 toabout 0.2:1.
 15. The method of claim 1, wherein the synergistic amountof hydrogen and the organozinc compound comprises a hydrogen:organozinccompound molar ratio in a range from about 100:1 to about 25,000:1. 16.The method of claim 1, wherein: a Mn of the olefin polymer issubstantially unchanged; a ratio of Mw/Mn of the olefin polymer isreduced by at least 75%; the Mw of the olefin polymer is reduced by atleast 75%; the Mw of the olefin polymer is reduced to less than about200,000 g/mol; the MI of the olefin polymer is increased to at leastabout 1 g/10 min; or any combination thereof.
 19. An olefinpolymerization process, the process comprising: contacting a transitionmetal-based catalyst composition with an olefin monomer and optionallyan olefin comonomer under polymerization conditions, and in the presenceof a synergistic amount of hydrogen and an organozinc compound, toproduce an olefin polymer; wherein the transition metal-based catalystcomposition comprises (a) a transition metal compound; (b) anactivator-support comprising a solid oxide treated with anelectron-withdrawing anion; and (c) optionally, a co-catalyst; andwherein: a Mw of the olefin polymer is less than about 200,000 g/mol; aMI of the olefin polymer is greater than about 1 g/10 min; or both. 20.The process of claim 19, wherein: the olefin monomer comprises ethylene;and the olefin comonomer comprises propylene, 1-butene, 1-pentene,1-hexene, 1-heptene, 1-octene, 1-decene, styrene, or a mixture thereof.21. The process of claim 19, wherein: a Mn of the olefin polymer issubstantially unchanged; and a ratio of Mw/Mn of the olefin polymer isreduced by at least 75%.
 22. The process of claim 19, wherein: thecatalyst composition is contacted with ethylene and an olefin comonomercomprising 1-butene, 1-hexene, 1-octene, or a mixture thereof the Mw ofthe olefin polymer is reduced to within a range from about 60,000 toabout 180,000 g/mol; and the MI of the olefin polymer is increased towithin a range from about 1.5 to about 20 g/10 min.
 23. A method ofcontrolling a polymerization reaction in a polymerization reactorsystem, the method comprising: (i) introducing a transition metal-basedcatalyst composition, an olefin monomer, and optionally an olefincomonomer into a polymerization reactor within the polymerizationreactor system, wherein the transition metal-based catalyst compositioncomprises (a) a transition metal compound; (b) an activator-supportcomprising a solid oxide treated with an electron-withdrawing anion; and(c) optionally, a co-catalyst; (ii) contacting the transitionmetal-based catalyst composition with the olefin monomer and theoptional olefin comonomer under polymerization conditions to produce anolefin polymer; and (iii) introducing a synergistic amount of hydrogenand an organozinc compound into the polymerization reactor system toreduce a weight-average molecular weight (Mw) and/or to increase a meltindex (MI) of the olefin polymer; wherein: the synergistic amount ofhydrogen and the organozinc compound comprises a hydrogen:organozinccompound molar ratio in a range from about 100:1 to about 25,000:1; anda Mn of the olefin polymer is substantially unchanged and/or a ratio ofMw/Mn of the olefin polymer is reduced by at least 75%.
 24. The methodof claim 23, wherein: the catalyst composition is contacted withethylene and an olefin comonomer comprising 1-butene, 1-hexene,1-octene, or a mixture thereof; the catalyst composition comprises anorganoaluminum co-catalyst; and the activator-support comprisesfluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or any combination thereof.
 25. The method of claim 24,wherein: the organozinc compound comprises diethylzinc; and thepolymerization reactor system comprises a slurry reactor.